Polar-group-containing olefin copolymer, polar-group-containing multinary olefin copolymer, olefin-based resin composition, and adhesive and layered product each using the same

ABSTRACT

A polar-group-containing olefin copolymer which comprises 99.999 to 80 mol % of structural units derived from at least one of ethylene and α-olefin having 3 to 20 carbon atoms and 20 to 0.001 mol % of structural units derived from at least one polar-group-containing monomer which contains an epoxy group and is represented by the structural formula (I) or structural formula (II), the polar-group-containing olefin copolymer being a random copolymer obtained by copolymerization in the presence of a transition metal catalyst and having a linear molecular structure.

TECHNICAL FIELD

The present invention relates to a polar-group-containing olefincopolymer having excellent properties, a multinary polar olefincopolymer, an olefin-based resin composition including thepolar-group-containing olefin copolymer and an olefin-based resin, alayered product using any of these, and various composited productsusing the same. More particularly, the invention relates to apolar-group-containing olefin copolymer which has a specific polar groupand shows excellent adhesiveness to various base materials, a multinarypolar olefin copolymer, an olefin-based resin composition including thepolar-group-containing olefin copolymer and an olefin-based resin, andan adhesive and a layered product which both take advantage of theadhesiveness.

BACKGROUND ART

In general, olefin-based resins have high mechanical strength and areexcellent in terms of impact resistance, long-term durability, chemicalresistance, corrosion resistance, etc., are inexpensive, and haveexcellent moldability. In addition, the resins are capable ofaccommodating environmental issues and recycling of resources.Olefin-based resins are hence used as important industrial materials.For example, the resins are molded into films, layered products,vessels, blow-molded bottles, etc. by injection molding, extrusionmolding, blow molding, etc., and are in use in a wide range ofapplications. Furthermore, properties such as, for example, gas barrierproperties can be imparted, besides those properties, by laminating theresins with a base such as a gas-barrier material, e.g., anethylene/vinyl alcohol copolymer (EVOH) or an aluminum foil. Thus,packaging materials or vessels having high functions can be obtained.

However, olefin polymers are generally nonpolar and have a drawback thatwhen used as laminating materials, the olefin polymers show exceedinglylow strength of adhesion to highly polar materials of different kinds,such as other synthetic resins, metals, and wood, or do not adhere tosuch materials.

Consequently, for improving the adhesiveness to highly polar materialsof different kinds, a technique in which a polar-group-containingmonomer is grafted using an organic peroxide is being practicedextensively (see, for example, patent document 1).

This technique, however, arouses a problem in that the olefin-basedresin undergoes intermolecular crosslinking, molecular-chain cleavage,etc. simultaneously with the grafting reaction and, hence, the graftmodification product does not retain the excellent properties of theolefin-based resin. For example, the intermolecular crosslinkingintroduces unnecessary long-chain branches to result in an increase inmelt viscosity and a widened molecular-weight distribution and inadverse influences on adhesiveness and moldability. In addition, themolecular-chain cleavage results in an increase in the content oflow-molecular-weight components in the olefin-based resin, therebyposing a problem in that gumming and fuming occur during molding.

Furthermore, the adhesiveness to highly polar materials of differentkinds can be increased by heightening the content of polar groups in thepolar-group-containing olefin copolymer. However, it is not easy tograft a polar-group-containing monomer in a large amount onto anolefin-based resin by graft modification. As a method for increasing thecontent of a polar-group-containing monomer, use may be made of, forexample, a method in which the amounts of a polar-group-containingmonomer and an organic peroxide which are to be subjected to a graftmodification are increased. Use of this method leads to the occurrenceof enhanced intermolecular crosslinking and molecular-chain cleavage inthe olefin-based resin to impair various properties, e.g., mechanicalproperties, impact resistance, long-term durability, and moldability. Inaddition, the polar-group-containing monomer remains unreacted in anincreased amount in the olefin-based resin and products of decompositionof the organic peroxide also remain in an increased amount in the resin,thereby arousing a trouble that deterioration of the olefin-based resinis accelerated or an unpleasant odor is emitted. Because of this, theattempt to heighten the content of a polar-group-containing monomer inan olefin-based resin, by itself, has had limitations.

Meanwhile, a method in which ethylene is copolymerized with apolar-group-containing monomer to obtain a polar-group-containing olefincopolymer using a high-pressure radical polymerization process has beendisclosed as a means for obtaining an olefin-based resin having apolar-group-containing monomer introduced thereinto, without causingintermolecular crosslinking, gelation, or molecular-chain cleavage tothe olefin-based resin (see patent documents 2 to 4). An example of themolecular structure of a polar-group-containing olefin copolymer intowhich polar groups have been introduced using a high-pressure radicalpolymerization process is shown in FIG. 1. According to this method, theproblems which arise due to graft modification are overcome and it ispossible to heighten the content of the polar-group-containing monomerin a polar-group-containing olefin copolymer as compared with graftmodification. However, since the polymerization process is ahigh-pressure radical process, the polar-group-containing olefincopolymer obtained has a molecular structure which randomly has a largenumber of long-chain branches and short-chain branches. Because of this,the polar-group-containing olefin copolymers obtained by this methodhave been limited to ones which have a low modulus of elasticity and lowmechanical properties as compared with the polar-group-containing olefincopolymers obtained by polymerization using a transition metal catalyst,and have been usable in limited applications where high strength isrequired.

On the other hand, in cases when a metallocene catalyst which hashitherto been in general use is used to copolymerize ethylene with apolar-group-containing monomer, this polymerization has been regarded asdifficult due to a decrease in catalytic activity in the polymerization.In recent years, however, methods have been proposed in which apolar-group-containing olefin copolymer is produced by polymerization inthe presence of a catalyst constituted of a transition metal and aspecific ligand coordinated thereto (see patent documents 5 to 8).According to these methods, a copolymer having an increased polar-groupcontent and having a high modulus of elasticity and high mechanicalstrength as compared with the polar-group-containing olefin copolymerobtained by a high-pressure radical process can be obtained. (FIG. 2 andFIG. 3 show images of the molecular structures of polar-group-containingolefin copolymers obtained by polymerization using a transition metalcatalyst.) The methods described in these documents are mainly intendedfor the production of copolymers of an acrylate-group-containingmonomer, such as methyl acrylate or ethyl acrylate, or a monomercontaining a specific polar group, such as vinyl acetate, with ethyleneor an α-olefin, and polar-group-containing olefin copolymers havingthese functional groups show insufficient adhesiveness to highly polarmaterials of different kinds.

Those patent documents include no statement concerning specificadhesiveness to highly polar materials of different kinds, and a featurewherein an olefin copolymer containing a specific polar group is usedfor the purpose of adhesiveness is disclosed in none of those documents.

Meanwhile, epoxy group is generally known as a polar group capable ofproducing excellent adhesiveness to highly polar materials of differentkinds. However, it is difficult to copolymerize anepoxy-group-containing comonomer by ordinary catalytic polymerizationprocesses, and the epoxy-group-containing polar olefin copolymers whichare presently on the market are mainly ones produced by high-pressureradical polymerization processes.

Disclosed as an example of polar-group-containing olefin copolymersproduced by polymerization without using a high-pressure radicalpolymerization process is a polar-group-containing olefin copolymerobtained by copolymerizing 1,2-epoxy-9-decene, ethylene, and 1-butene inan invention concerning a production process, which is a so-calledmasking process, wherein polymerization is conducted in the presence ofa specific metallocene-based catalyst and a sufficient amount of anorganoaluminum (the amount being at least equimolar with thepolar-group-containing monomer) (see patent document 9).

According to that invention, however, an organoaluminum is necessary ina large amount for copolymerizing the polar-group-containing olefin andthis necessarily results in an increase in production cost. In addition,the organoaluminum used in a large amount comes to be present as animpurity in the polar-group-containing olefin copolymer to cause adecrease in mechanical property, discoloration, and accelerateddeterioration, and removing these troubles leads to a further costincrease. Moreover, the main effect of that invention is to produce apolar-group-containing olefin copolymer while attaining high activity inpolymerization, and the patent document includes no statement concerningspecific adhesiveness to highly polar materials of different kinds. Inaddition, that patent document includes no statement at all concerningresin properties which are necessary for a polar-group-containing olefincopolymer to have for obtaining sufficient adhesiveness to highly polarmaterials of different kinds, and a feature wherein apolar-group-containing olefin copolymer is used for the purpose of highadhesiveness is not disclosed therein.

It can be seen from the prior-art techniques described above that therehas been a desire for a proposal on a polar-group-containing olefincopolymer that contains epoxy groups and is produced by a process whichis none of the processes each having one or more problems, such as graftmodification, which is a process for introducing polar groups into anolefin copolymer, the high-pressure radical polymerization process, andthe process in which an organoaluminum is used in a large amount, andthat shows excellent adhesiveness to highly polar materials of differentkinds, and on a layered product which includes thepolar-group-containing olefin copolymer.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: JP-A-50-004144

Patent Document 2: Japanese Patent No. 2516003

Patent Document 3: JP-A-47-23490

Patent Document 4: JP-A-48-11388

Patent Document 5: JP-A-2010-202647

Patent Document 6: JP-A-2010-150532

Patent Document 7: JP-A-2010-150246

Patent Document 8: JP-A-2010-260913

Patent Document 9: Japanese Patent No. 4672214

SUMMARY OF THE INVENTION Problems that the Invention is to Solve

An object of the invention, in view of the conventional problemsdescribed above under Background Art, is to develop: apolar-group-containing olefin copolymer which shows excellentadhesiveness to highly polar materials of different kinds and which isproduced by a process that is none of the conventional processes eachhaving one or more problems; a multinary polar olefin copolymer; and anolefin-based resin composition including the polar-group-containingolefin copolymer and an olefin-based resin. Another subject for theinvention is to provide an adhesive, a layered product, various moldedarticles, and various composited products, which each using the same.

Means for Solving the Problems

The present inventors variously took consideration and made closeinvestigations for demonstration with regard to methods for introducinga polar group, selection of a polar group and a polymerization catalyst,molecular structures of polar-group-containing olefin copolymers,correlation between the structure of a copolymer and the adhesivenessthereof, etc. in order to produce a polar-group-containing olefincopolymer by a simple and efficient process and improve the adhesivenessof the copolymer to materials of different kinds and in order to therebyovercome the problems described above. As a result, the inventors wereable to discover a polar-group-containing olefin copolymer havingexcellent adhesiveness to various materials of different kinds, amultinary polar olefin copolymer, and an olefin-based resin compositionincluding the polar-group-containing olefin copolymer and anolefin-based resin. The present invention has been thus accomplished.

A first aspect of the present invention is a polymer which is an olefincopolymer (A) having a specific polar group and obtained bypolymerization using a transition metal catalyst, and which ischaracterized by showing remarkably excellent adhesiveness and beingexcellent in terms of various properties, so long as the content of apolar-group-containing monomer is in a specific range.

A second aspect of the invention is a polymer which is a multinary polarolefin copolymer (B) having an exceedingly narrow molecular-weightdistribution within a specific range and having a melting point within aspecific range, and which is characterized by showing a markedimprovement in balance between adhesiveness and mechanical properties.

Furthermore, a third aspect of the invention is an olefin-based resincomposition (D) which has been obtained by adding an olefin-based resin(C) in a specific proportion to a polar-group-containing olefincopolymer (A′) and which has been thus made to have the excellentproperties possessed by the olefin-based resin and to retain thesufficient adhesiveness to highly polar materials of different kindswhich is possessed by the polar-group-containing olefin copolymer.

<<First Aspect>>

(1) A polar-group-containing olefin copolymer (A) which comprises 99.999to 80 mol % of structural units derived from at least one of ethyleneand α-olefin having 3 to 20 carbon atoms and 20 to 0.001 mol % ofstructural units derived from at least one polar-group-containingmonomer which contains an epoxy group and is represented by thefollowing structural formula (I) or following structural formula (II),the polar-group-containing olefin copolymer being a random copolymerobtained by copolymerization in the presence of a transition metalcatalyst and having a linear molecular structure:

(In structural formula (I), R¹ represents a hydrogen atom or an alkylgroup having 1 to 10 carbon atoms, and R², R³, and R⁴ each independentlyrepresent a hydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R² to R⁴being the following epoxy-group-containing specific functional group:

Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure comprising a carbon atom, an oxygenatom, and a hydrogen atom),

(In structural formula (II), R⁵ to R⁸ each independently represent ahydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R⁵ to R⁸being the following epoxy-group-containing specific functional group,and m is 0 to 2:

Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure comprising a carbon atom, an oxygenatom, and a hydrogen atom)

(2) The polar-group-containing olefin copolymer (A) according to the(1), which has a melting point of 50 to 140° C., the melting point beingthe temperature corresponding to a maximum peak in an endothermic curvedetermined by differential scanning calorimetry (DSC).(3) The polar-group-containing olefin copolymer (A) according to the (1)or (2), wherein the amount of aluminum (Al) in thepolar-group-containing olefin copolymer is 0 to 100,000 μg per g of thecopolymer.(4) The polar-group-containing olefin copolymer (A) according to any oneof the (1) to (3), which has a weight-average molecular weight (Mw), asdetermined by gel permeation chromatography (GPC), of 1,000 to2,000,000.(5) The polar-group-containing olefin copolymer (A) according to any oneof the (1) to (4), which has a weight-average molecular weight (Mw), asdetermined by gel permeation chromatography (GPC), of 33,000 to2,000,000.(6) The polar-group-containing olefin copolymer (A) according to any oneof the (1) to (5), wherein the transition metal catalyst is a transitionmetal which comprises a chelatable ligand and a Group-5 to Group-11metal.(7) The polar-group-containing olefin copolymer (A) according to any oneof the (1) to (6), wherein the polar-group-containing olefin copolymeris a transition metal catalyst comprising: palladium or nickel metal;and a triarylphosphine or triarylarsine compound coordinated thereto.

<<Second Aspect>>

(8) A polar-group-containing multinary olefin copolymer (B) comprising:units of one or more nonpolar monomers (X1) selected from ethylene andα-olefins having 3 to 10 carbon atoms; units of one or more polarmonomers (Z1) selected from monomers having an epoxy group; and units ofany one or more non-cyclic or cyclic monomers (Z2) (with the provisothat at least one kind of units of X1, at least one kind of units of Z1,and at least one kind of units of Z2 are essentially contained), thepolar-group-containing multinary olefin copolymer being a randomcopolymer obtained by copolymerization in the presence of a transitionmetal catalyst and having a linear molecular structure.(9) The polar-group-containing multinary olefin copolymer (B) accordingto the (8), which has a ratio of weight-average molecular weight (Mw) tonumber-average molecular weight (Mn), as determined by gel permeationchromatography (GPC), in the range of 1.5 to 3.5.(10) The polar-group-containing multinary olefin copolymer (B) accordingto (8) or (9), which has a melting point Tm (° C.) satisfying50<Tm<128−6.0[Z1] (wherein [Z1] (mol %) is monomer units derived fromZ1), the melting point being the temperature corresponding to a maximumpeak in an endothermic curve determined by differential scanningcalorimetry (DSC).(11) The polar-group-containing multinary olefin copolymer (B) accordingto any one of the (8) to (10), wherein the content of the units of oneor more polar monomers (Z1) selected from monomers having an epoxy groupis 0.001 to 20.000 mol %.(12) The polar-group-containing multinary olefin copolymer (B) accordingto any one of the (8) to (11), wherein the units of one or more nonpolarmonomers (X1) are ethylene units.(13) The polar-group-containing multinary olefin copolymer (B) accordingto any one of the (8) to (12), wherein the transition metal catalyst isa transition metal which comprises a chelatable ligand and a Group-5 toGroup-11 metal.(14) The polar-group-containing multinary olefin copolymer (B) accordingto any one of the (8) to (13), wherein the polar-group-containingmultinary olefin copolymer is a transition metal catalyst comprising:palladium or nickel metal; and a triarylphosphine or triarylarsinecompound coordinated thereto.

<<Third Aspect>>

(15) An olefin-based resin composition (D) comprising: apolar-group-containing olefin copolymer (A′) and an olefin-based resin(C), the polar-group-containing olefin copolymer (A′) being a randomcopolymer having a linear molecular structure and obtained bycopolymerizing at least one of ethylene and α-olefin having 3 to 20carbon atoms with a polar-group-containing monomer containing an epoxygroup in the presence of a transition metal catalyst, wherein the amountof the olefin-based resin (C) incorporated is 1 to 99,900 parts byweight per 100 parts by weight of the polar-group-containing olefincopolymer (A′).(16) The olefin-based resin composition (D) according to the (15),wherein the polar-group-containing monomer containing an epoxy group isa polar-group-containing monomer containing an epoxy group, representedby the following structural formula (I) or following structural formula(II):

(In structural formula (I), R¹ represents a hydrogen atom or an alkylgroup having 1 to 10 carbon atoms, and R², R³, and R⁴ each independentlyrepresent a hydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R² to R⁴being the following epoxy-group-containing specific functional group,

Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure comprising a carbon atom, an oxygenatom, and a hydrogen atom),

(In structural formula (II), R⁵ to R⁸ each independently represent ahydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R⁵ to R⁸being the following epoxy-group-containing specific functional group,and m is 0 to 2:

Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure comprising a carbon atom, an oxygenatom, and a hydrogen atom)

(17) The olefin-based resin composition (D) according to the (15) or(16), wherein in the polar-group-containing olefin copolymer (A′), theamount of structural units derived from at least one of ethylene andα-olefin having 3 to 20 carbon atoms is 99.999 to 80 mol % and theamount of structural units derived from the polar-group-containingmonomer containing an epoxy group is 20 to 0.001 mol %.(18) The olefin-based resin composition (D) according to any one of the(15) to (17), wherein the olefin-based resin (C) is at least one of ahomopolymer and a copolymer, the homopolymer and the copolymer beingobtained by polymerizing a monomer selected from at least one ofethylene and α-olefin having 3 to 20 carbon atoms.(19) The olefin-based resin composition (D) according to the (15) to(18), wherein the olefin-based resin (C) is either an ethylenehomopolymer or a copolymer of ethylene with α-olefin having 3 to 20carbon atoms.(20) The olefin-based resin composition (D) according to any one of (15)to (19), wherein the polar-group-containing olefin copolymer (A′) has amelting point in the range of 50 to 140° C., the melting point being thetemperature corresponding to a maximum peak in an endothermic curvedetermined by differential scanning calorimetry (DSC).(21) The olefin-based resin composition (D) according to any one of the(15) to (20), wherein the polar-group-containing olefin copolymer (A′)is a copolymer obtained by polymerization in the presence of atransition metal catalyst of a Group-5 to Group-11 metal having achelatable ligand.(22) The olefin-based resin composition (D) according to any one of (15)to (21), wherein the polar-group-containing olefin copolymer (A′) is acopolymer obtained by polymerization in the presence of a transitionmetal catalyst which comprises palladium or nickel metal and atriarylphosphine or triarylarsine compound coordinated thereto.(23) The olefin-based resin composition (D′) according to any one of the(15) to (22), wherein the olefin-based resin (C) has a density, asmeasured in accordance with JIS K7112, in the range of 0.890 to 1.20g/cm³.(24) The olefin-based resin composition (D′) according to any one of the(15) to (23), wherein the olefin-based resin (C) has a melting point inthe range of 90 to 170° C., the melting point being the temperaturecorresponding to a maximum peak in an endothermic curve determined bydifferential scanning calorimetry (DSC).(25) The olefin-based resin composition (D′) according to any one of the(15) to (24), wherein the melting point, which is the temperaturecorresponding to a maximum peak in an endothermic curve determined bydifferential scanning calorimetry (DSC), is in the range of 119 to 170°C.(26) The olefin-based resin composition (D′) according to any one of the(15) to (25), which has a heat of fusion ΔH, as determined bydifferential scanning calorimetry (DSC), in the range of 80 to 300 J/g.(27) The olefin-based resin composition (D″) according to any one of the(15) to (22), wherein the olefin-based resin (C) has a melting point inthe range of 30 to 124° C., the melting point being the temperaturecorresponding to a maximum peak in an endothermic curve determined bydifferential scanning calorimetry (DSC).

Further, the present invention relates to an adhesive, a layeredproduct, and product of the other uses, which comprise at least one ofthe polar-group-containing olefin copolymer (A) (the First Aspect), thepolar-group-containing multinary olefin copolymer (B) (the SecondAspect), and the olefin-based resin composition (D), the olefin-basedresin composition (D′), and the olefin-based resin composition (D″) (theThird Aspect). The details are set forth below.

(28) An adhesive which comprises the polar-group-containing olefincopolymer (A) according to any one of the (1) to (7), thepolar-group-containing multinary olefin copolymer (B) according to anyone of the (8) to (14), or, the olefin-based resin composition (D), theolefin-based resin composition (D′) or the olefin-based resincomposition (D″) according to any one of (15) to (27).(29) A layered product which comprises: the polar-group-containingolefin copolymer (A) according to any one of the (1) to (7), thepolar-group-containing multinary olefin copolymer (B) according to anyone of the (8) to (14), or, the olefin-based resin composition (D), theolefin-based resin composition (D′) or the olefin-based resincomposition (D″) according to any one of (15) to (27); and a base layer.(30) The layered product according to the (29), wherein the base layercomprises at least one member selected from olefin-based resins, highlypolar thermoplastic resins, metals, vapor-deposited films of inorganicoxide, paper, cellophane, woven fabric, and nonwoven fabric.(31) The layered product according to the (29) or (30), wherein the baselayer comprises at least one member selected from polyamide-basedresins, fluororesins, polyester-based resins, and ethylene/vinyl alcoholcopolymers (EVOH).

Effects of the Invention

The polar-group-containing olefin copolymer (A) as the first aspect ofthe invention shows high adhesiveness to other bases since thiscopolymer has a specific molecular structure and resin properties; themultinary polar olefin copolymer (B) as the second aspect of theinvention shows high adhesiveness to other bases since this copolymerhas an exceedingly narrow molecular-weight distribution within aspecific range and has a melting point within a specific range; and thethird aspect of the invention has been accomplished by adding each ofolefin-based resins (C), in a specific proportion, to thepolar-group-containing olefin copolymer (A′) to thereby give anolefin-based resin composition (D), an olefin-based resin composition(D′), and an olefin-based resin composition (D″) which each show highadhesiveness to other bases. Thus, the present invention has made itpossible to produce industrially useful layered products and compositedmaterials. This noticeable effect has been demonstrated by the dataobtained in the Examples of the invention which will be given later andby comparisons between the Examples and the Comparative Examples.

The polar-group-containing olefin copolymer (A) according to theinvention, the multinary polar olefin copolymer (B) according to theinvention, and the olefin-based resin composition (D), olefin-basedresin composition (D′), and olefin-based resin composition (D″)according to the invention, which each include thepolar-group-containing olefin copolymer and an olefin-based resin, areexcellent in terms of not only adhesiveness but also mechanical andthermal property and further have chemical resistance. These copolymersand compositions are hence applicable as useful multilayered moldedobjects, and are usable in a wide range of various applications afterbeing molded into multilayered films, blow-molded multilayered bottles,etc. by, for example, extrusion molding, blow molding, etc.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a drawing which shows an image of the molecular structure ofan olefin copolymer produced through polymerization by a high-pressureradical polymerization process.

FIG. 2 is a drawing which shows an image of the molecular structure ofan olefin copolymer produced by polymerization using a metalliccatalyst, the copolymer having no long-chain branch.

FIG. 3 is a drawing which shows an image of the molecular structure ofan olefin copolymer produced by polymerization using a metalliccatalyst, the copolymer having a small amount of long-chain branches.

FIG. 4 is a graph which shows a relationship between the proportion of apolar-group-containing olefin copolymer (A′-3-1) and the strength ofadhesion to a polyamide.

FIG. 5 is a graph which shows a relationship between the proportion of apolar-group-containing olefin copolymer (A′-3-9) and the strength ofadhesion to a polyamide.

FIG. 6 is a graph which shows a relationship between the proportion of apolar-group-containing olefin copolymer (A′-3-2) and the strength ofadhesion to a polyamide.

FIG. 7 is a graph which shows a relationship between the proportion of apolar-group-containing olefin copolymer (A′-3-3) and the strength ofadhesion to a polyamide.

FIG. 8 is a graph which shows a relationship between the proportion of apolar-group-containing olefin copolymer (A′-3-5) and the strength ofadhesion to a polyamide.

FIG. 9 is a graph which shows a relationship between the proportion of apolar-group-containing olefin copolymer (A′-3-4) and the strength ofadhesion to a fluororesin.

FIG. 10 is a graph which shows a relationship between the proportion ofa polar-group-containing olefin copolymer (A′-3-9) and the strength ofadhesion to a fluororesin.

MODES FOR CARRYING OUT THE INVENTION

Detailed explanations are given below on each of thepolar-group-containing olefin copolymer (A) of the invention, themultinary polar olefin copolymer (B) of the invention, the olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) of the invention, which each includethe polar-group-containing olefin copolymer and an olefin-based resin,and the adhesive and layered product of the invention, which eachinclude any of these copolymers and compositions.

[I] with Respect to Polar-Group-Containing Olefin Copolymer (A)

(1) Polar-Group-Containing Olefin Copolymer (A)

The polar-group-containing olefin copolymer according to the inventionis a copolymer of ethylene or at least one α-olefin having 3 to 20carbon atoms with at least one epoxy-group-containing monomer, thecopolymer being a random copolymer in which units of the monomers havebeen randomly copolymerized and which has a substantially linearmolecular structure.

The polar-group-containing olefin copolymer (A) according to theinvention is characterized by being obtained by polymerizing ethyleneand/or α-olefin having 3 to 20 carbon atoms with at least oneepoxy-group-containing monomer in the presence of a transition metalcatalyst. The ethylene or α-olefin having 3 to 20 carbon atoms which isto be subjected to the polymerization is not particularly limited.Preferably, however, ethylene is essentially included, and one or moreα-olefins having 3 to 20 carbon atoms may be further included accordingto need. Although ethylene or one of α-olefins having 3 to 20 carbonatoms may be subjected alone to the polymerization, two or more thereofmay be used. Furthermore, other monomers having no polar group may befurther subjected to the polymerization so long as the use thereof doesnot depart from the spirit of the invention. It is desirable that theproportion of structural units derived from ethylene and/or at least oneof the α-olefins should be selected from the range of usually 80 to99.999 mol %, preferably 85 to 99.99 mol %, more preferably 90 to 99.98mol %, even more preferably 95 to 99.97 mol %.

(2) α-Olefins

The α-olefins according to the invention are α-olefins having 3 to 20carbon atoms and represented by the structural formula CH₂═CHR¹⁸ (R¹⁸ isa hydrocarbon group which has 1 to 18 carbon atoms and may have a linearstructure or have a branch). More preferred are α-olefins having 3 to 12carbon atoms. Even more preferred are one or more α-olefins selectedfrom propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,3-methyl-1-butene, and 4-methyl-1-pentene. More suitable are one or moreα-olefins selected from propylene, 1-butene, 1-hexene, and 1-octene. Oneα-olefin may be subjected alone to the polymerization, or two or moreα-olefins may be subjected to the polymerization.

(3) Monomers Having No Polar Group

The monomers having no polar group, in the invention, are notparticularly limited so long as the monomers are ones which each haveone or more carbon-carbon double bonds in the molecular structure and inwhich the molecule is configured of carbon and hydrogen as the onlyelements. Examples thereof include dienes, trienes, aromatic vinylmonomers, and cycloolefins. Preferred are butadiene, isoprene, styrene,vinylcyclohexane, cyclohexene, vinylnorbornene, and norbornene.

(4) Polar-Group-Containing Monomers

The polar-group-containing monomers according to the invention need tocontain an epoxy group. So long as an olefin-based resin compositionincludes a polar-group-containing olefin copolymer which has epoxygroups, this composition can be laminated and bonded to bases made ofhighly polar thermoplastic resins, such as polyamide resins, polyesterresins, ethylene/vinyl alcohol copolymers (EVOH), or fluororesins havingbondability imparted thereto, and to bases made of metallic materialssuch as aluminum and steel.

The polar-group-containing monomers according to the inventionpreferably are monomers which contain an epoxy group and are representedby the following structural formula (I) or structural formula (II).

(In structural formula (I), R¹ represents a hydrogen atom or an alkylgroup having 1 to 10 carbon atoms, and R², R³, and R⁴ each independentlyrepresent a hydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R² to R⁴being the following epoxy-group-containing specific functional group.Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure including a carbon atom, an oxygenatom, and a hydrogen atom)

(In structural formula (II), R⁵ to R⁸ each independently represent ahydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R⁵ to R⁸being the following epoxy-group-containing specific functional group,and m is 0 to 2.Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure including a carbon atom, an oxygenatom, and a hydrogen atom)

The molecular structures of such polar-group-containing monomers are notparticularly limited. However, the polar-group-containing monomersrepresented by structural formula (I) are more preferred whencopolymerizability in the presence of a transition metal catalyst, thehandleability of the polar-group-containing monomers, etc. are takeninto account. More preferred are polar-group-containing monomersrepresented by structural formula (I) wherein R¹ is a hydrogen atom oran alkyl group having 1 to 10 carbon atoms, R², R³, and R⁴ are eachindependently any of a hydrogen atom, a hydrocarbon group, and thefollowing epoxy-group-containing specific functional group, any one ofR² to R⁴ being the epoxy-group-containing specific functional group.

(Specific functional group: a group which essentially contains an epoxygroup and further essentially contains any of a hydrocarbon group, acarbonyl group, and an ether group and which has a molecular structureincluding a carbon atom, an oxygen atom, and a hydrogen atom)

Examples of the polar-group-containing monomers represented bystructural formula (I) or structural formula (II) include w-alkenylepoxides such as 5-hexene epoxide, 6-heptene epoxide, 7-octene epoxide,8-nonene epoxide, 9-decene epoxide, 10-undecene epoxide, and 11-dodeceneepoxide, w-alkenyl epoxides having a branch in the molecular structure,such as 2-methyl-6-heptene epoxide, 2-methyl-7-octene epoxide,2-methyl-8-nonene epoxide, 2-methyl-9-decene epoxide, and2-methyl-10-undecene epoxide, unsaturated glycidyl ethers such as allyglycidyl ether, 2-methylallyl glycidyl ether, o-allylphenol glycidylether, m-allylphenol glycidyl ether, and p-allylphenol glycidyl ether,glycidyl esters of unsaturated carboxylic acids such as4-hydroxybutyl(meth)acrylate, acrylic acid, methacrylic acid, glycidylp-styrylcarboxylate, endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylicacid, endo-cis-bicyclo[2,2,1]hept-5-ene-2-methyl-2,3-dicarboxylic acid,itaconic acid, citraconic acid, and butenetricarboxylic acid,cycloolefins containing an epoxy group, such as epoxyhexylnorbornene,epoxycyclohexanenorbornene, and methyl glycidyl ether norbornene, andother epoxy-group-containing monomers such as 2-(o-vinylphenyl)ethyleneoxide, 2-(p-vinylphenyl)ethylene oxide, 2-(o-allylphenyl)ethylene oxide,2-(p-allylphenyl)ethylene oxide, 2-(o-vinylphenyl)propylene oxide,2-(p-vinylphenyl)propylene oxide, 2-(o-allylphenyl)propylene oxide,2-(p-allylphenyl)propylene oxide, p-glycidylstyrene, 3,4-epoxy-1-butene,3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene,3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexenemonoxide, allyl 2,3-epoxycyclopentyl ether, 2,3-epoxy-5-vinylnorbornane,and 1,2-epoxy-4-vinylcyclohexane. Especially preferred of these are1,2-epoxy-9-decene, 4-hydroxybutyl acrylate glycidyl ether, glycidylmethacrylate, 1,2-epoxy-4-vinylcyclohexane, which are represented by thefollowing structural formulae, and the like.

One epoxy-group-containing monomer may be subjected alone to thepolymerization, or two or more epoxy-group-containing monomers may beused in combination.

There are cases where the polar-group-containing olefin copolymer (A),for which a monomer containing an epoxy group was used, undergoesintermolecular crosslinking due to the reaction between epoxy groupscontained therein. The intermolecular crosslinking may be allowed toproceed so long as this crosslinking does not depart from the spirit ofthe invention.

(5) Structural Units of Polar-Group-Containing Olefin Copolymer (A)

The structural units of the polar-group-containing olefin copolymeraccording to the invention and the amounts of the structural units areexplained.

The structure derived from one molecule of either ethylene or anα-olefin having 3 to 20 carbon atoms and the structure derived from onemolecule of an epoxy-group-containing monomer are each defined as onestructural unit within the polar-group-containing olefin copolymer. Theproportion, in terms of mol %, of each structural unit in thepolar-group-containing olefin copolymer is the amount of the structuralunit.

(6) Amount of Structural Unit of Polar-Group-Containing Monomer

The amount of structural units derived from an epoxy-group-containingmonomer in the polar-group-containing olefin copolymer (A) according tothe invention is selected from the range of usually 20 to 0.001 mol %,preferably 15 to 0.01 mol %, more preferably 10 to 0.02 mol %,especially preferably 5 to 0.03 mol %. It is preferable that suchstructural units should be always present in the polar-group-containingolefin copolymer of the invention. In case where the amount ofstructural units derived from an epoxy-group-containing monomer is lessthan that range, the adhesiveness to highly polar materials of differentkinds is insufficient. In case where the amount thereof is larger thanthat range, sufficient mechanical properties are not obtained.

(7) Method for Determining the Amount of Structural Unit ofPolar-Group-Containing Monomer

The amount of polar-group structural units in the polar-group-containingolefin copolymer (A) according to the invention is determined using a¹H-NMR spectrum. The ¹H-NMR spectrum was obtained by the followingmethod. A specimen was introduced, in an amount of 200 to 250 mg, intoan NMR sample tube having an inner diameter of 10 mm together with 2.4mL of o-dichlorobenzene/deuterated bromobenzene (C₆D₅Br)=4/1 (by volume)and with hexamethyldisiloxane as a chemical-shift reference substance.This sample tube was subjected to nitrogen displacement and then closed.The specimen was dissolved by heating to obtain an even solution, whichwas subjected to NMR spectroscopy. The NMR spectroscopy was performed at120° C. using NMR apparatus Type AV400M, manufactured by Bruker BiospinK.K., to which a cryoprobe having a diameter of 10 mm had been attached.The ¹H-NMR examination was made under the conditions of a pulse angle of1° and a pulse interval of 1.8 seconds, the number of integrations being1,024 or more. Chemical shifts were set so that the peak for the methylprotons of hexamethyldisiloxane was at 0.088 ppm, and the chemicalshifts for other kinds of protons were determined using that chemicalshift as a reference. A ¹³C-NMR examination was made by the completeproton decoupling method under the conditions of a pulse angle of 90°and a pulse interval of 20 seconds, the number of integrations being 512or more. Chemical shifts were set so that the peak for the methyl carbonof hexamethyldisiloxane was at 1.98 ppm, and the chemical shifts forother kinds of carbon atoms were determined using that chemical shift asa reference.

Amounts of the Structural Units of Polar-Group-Containing Monomers[Amount of Structural Unit of 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)]

The sum of the integrated intensities of peaks assigned to thepolar-group-containing olefin copolymer and appearing in the range of0.3 to 3.1 ppm was expressed by IA1, and the sum of the integratedintensities of peaks which were assigned to the protons of the 4-HBAGEcontained in the copolymer and which appeared at 2.4, 2.6, 3.0, 3.3,3.4, 3.5, and 4.1 ppm was expressed by IX1. The amount of the structuralunit was determined in accordance with the following equation.

Content of 4-HBAGE(mol%)=40×IX1/(IA1−0.6×IX1)

[Amount of Structural Unit of 1,2-Epoxy-9-Decene (C8-EPO)]

The sum of the integrated intensities of peaks assigned to thepolar-group-containing olefin copolymer (A) and appearing in the rangeof 0.3 to 3.1 ppm was expressed by IA2, and the sum of the integratedintensities of peaks which were assigned to the protons of the C8-EPOcontained in the copolymer and which appeared at 2.4, 2.6, and 2.8 ppmwas expressed by IX2. The amount of the structural unit was determinedin accordance with the following equation.

Content of C8-EPO(mol%)=(400/3)×IX2/(IA2−11/3×IX2)

[Amount of Structural Unit of 1,2-Epoxy-4-Vinylcyclohexane (EP-VCH)]

The sum of the integrated intensities of peaks assigned to thepolar-group-containing olefin copolymer and appearing in the range of0.3 to 3.2 ppm was expressed by IA2, and the sum of the integratedintensities of peaks which were assigned to the protons of the EP-VCHcontained in the copolymer and which appeared at around 3.0 ppm wasexpressed by IX2. The amount of the structural unit was determined inaccordance with the following equation.

Content of EP-VCH(mol%)=100×IX2/(0.5×IA2−2×IX2)

[Amount of Structural Unit of Glycidyl Methacrylate (GMA)]

The sum of the integrated intensities of peaks assigned to thepolar-group-containing olefin copolymer (A) and appearing in the rangeof 0.3 to 3.2 ppm was expressed by IA3, and the sum of the integratedintensities of peaks which were assigned to the protons of the GMAcontained in the copolymer and which appeared at 2.5, 2.6, 3.1, 3.9, and4.3 ppm was expressed by IX3. The amount of the structural unit wasdetermined in accordance with the following equation.

Content of GMA(mol%)=80×IX3/(IA3−0.8×IX3)

(8) Molecular Structure of Polar-Group-Containing Olefin Copolymer (A)

The polar-group-containing olefin copolymer (A) according to theinvention is a random copolymer of ethylene and/or α-olefin having 3 to20 carbon atoms with at least one epoxy-group-containing monomer.

An example of the molecular structure of the polar-group-containingolefin copolymer (A) in the invention is shown in the followingparagraph. The term random copolymer means a copolymer in which, as inthe molecular-structure example shown in the following paragraph, theprobability that structural unit A or structural unit B is found at anyposition within the molecular chain is independent of the kind of thestructural unit which adjoins that structural unit. The molecular-chainterminals of the polar-group-containing olefin copolymer may be ethyleneand/or an α-olefin having 3 to 20 carbon atoms, or may be anepoxy-group-containing monomer. As shown below, the molecular structure(example) of the polar-group-containing olefin copolymer in theinvention is a random copolymer configured from ethylene or an α-olefinhaving 3 to 20 carbon atoms and from an epoxy-containing monomer.

-ABAAAABBAABAAA-  [Chem. 11]

A: ethylene or α-olefin having 3 to 20 carbon atoms

B: epoxy-group-containing monomer

Incidentally, the molecular structure (example) of an olefin copolymerinto which polar groups have been introduced by graft modification isshown below for reference. In this molecular structure, some of theolefin copolymer formed by copolymerizing ethylene or an α-olefin having3 to 20 carbon atoms has been graft-modified with anepoxy-group-containing monomer.

The polar-group-containing olefin copolymer (A) according to theinvention is characterized by being produced in the presence of atransition metal catalyst, and the molecular structure thereof islinear. An image of an olefin copolymer produced through polymerizationby a high-pressure radical polymerization process is shown as an examplein FIG. 1, while images of olefin copolymers produced by polymerizationusing a metallic catalyst are shown as examples in FIG. 2 and FIG. 3. Asapparent from the drawings, the molecular structures differ depending onthe production processes. Such differences in molecular structure can becontrolled by selecting a production process. However, as described in,for example, JP-A-2010-150532, the molecular structure of a copolymercan be presumed also from the complex modulus of elasticity measuredwith a rotary rheometer. More specifically, in the case where acopolymer, when examined with a rotary rheometer, has a complex modulusof elasticity wherein the phase angle δ(G*=0.1 MPa) at absolute valueG*=0.1 MPa is 40 degrees or larger, the molecular structure thereof is alinear structure such as that shown in FIG. 2 or FIG. 3. That is, thiscopolymer shows a structure which contains no long-chain branch at all(FIG. 2) or a structure which contains a small amount of long-chainbranches to such a degree as not to affect the mechanical strength (FIG.3). Meanwhile, in the case where a copolymer, when examined with arotary rheometer, has a complex modulus of elasticity wherein the phaseangle δ(G*=0.1 MPa) at absolute value G*=0.1 MPa is less than 40degrees, this copolymer shows a molecular structure which containslong-chain branches in too large an amount, such as that shown in FIG.1, and has poor mechanical strength. The phase angle δ at absolute valueG*=0.1 MPa in the complex modulus of elasticity determined with a rotaryrheometer is affected by both the molecular-weight distribution and thelong-chain branches. However, with respect only to copolymers in whichMw/Mn≦4, more preferably Mw/Mn≦3, the phase angle δ(G*=0.1 MPa) can bean index to the amount of long-chain branches; the larger the amount oflong-chain branches, the smaller the value of δ(G*=0.1 MPa).Incidentally, so long as Mw/Mn is 1.5 or larger, the value of δ(G*=0.1MPa) does not exceed 75 degrees even when the copolymer has nolong-chain branch.

(9) Weight-Average Molecular Weight (Mw) of Polar-Group-ContainingOlefin Copolymer (A)

It is desirable that the weight-average molecular weight (Mw) of thepolar-group-containing olefin copolymer (A) according to the inventionshould be in the range of usually 1,000 to 2,000,000, preferably 10,000to 1,500,000, more preferably 20,000 to 1,000,000, even more preferably31,000 to 800,000, especially preferably 33,000 to 800,000. In casewhere the Mw thereof is less than 1,000, this copolymer is insufficientin properties such as mechanical strength and impact resistance andshows poor adhesiveness to highly polar materials of different kinds. Incase where the Mw thereof exceeds 2,000,000, this copolymer hasexceedingly high melt viscosity and is difficult to mold.

The weight-average molecular weight (Mw) of the polar-group-containingolefin copolymer (A) according to the invention is determined by gelpermeation chromatography (GPC). The molecular-weight distributionparameter (Mw/Mn) is obtained by further determining the number-averagemolecular weight (Mn) by gel permeation chromatography (GPC) andcalculating the ratio between the Mw and the Mn, i.e., Mw/Mn.

A method of measurement by GPC according to the invention is as follows.(Measurement Conditions) Kind of apparatus used, 150 C, manufactured byWaters Inc.; detector, IR detector MIRAN 1A (measuring wavelength, 3.42μm), manufactured by FOXBORO Company; measuring temperature, 140° C.;solvent, o-dichlorobenzene (ODCB); columns, AD806M/S (three columns),manufactured by Showa Denko K.K.; flow rate, 1.0 mL/min; injectionamount, 0.2 mL

(Preparation of Specimen) A specimen is prepared as a 1-mg/mL solutionusing ODCB (containing 0.5 mg/mL BHT (2,6-di-t-butyl-4-methylphenol)),the copolymer being dissolved by heating at 140° C. for about 1 hour.(Calculation of Molecular Weights) Conversion from retention volume to amolecular weight is made by the standard polystyrene method using acalibration curve which has been drawn beforehand with standardpolystyrenes. The standard polystyrenes to be used are ones which havethe following trade names: F380, F288, F128, F80, F40, F20, F10, F4, F1,A5000, A2500, and A1000, all manufactured by Tosoh Corp. Solutionsobtained by dissolving these standard polystyrenes in ODCB (containing0.5 mg/mL BHT) each in a concentration of 0.5 mg/mL are injected each inan amount of 0.2 mL to draw a calibration curve. The calibration curveis approximated by the least square method, and the resultant cubicequation is used. For the viscosity equation [η]=K×Mα for use inconversion into the molecular weight, the following numerals are used.

PS:K=1.38×10−4,α=0.7

PE:K=3.92×10−4,α=0.733

PP:K=1.03×10−4,α=0.78

(10) Melting Point of Polar-Group-Containing Olefin Copolymer (A)

The melting point of the olefin-based resin (A) according to theinvention is expressed in terms of the maximum-peak temperature in anendothermic curve determined with a differential scanning calorimeter(DSC). In the case where the endothermic curve, which is obtained byplotting heat flow (mW) as ordinate and temperature (° C.) as abscissain a DSC examination, shows a plurality of peaks, the term maximum-peaktemperature means the temperature corresponding to the peak which is thehighest among these in terms of height from the base line. In the casewhere the endothermic curve shows only one peak, that term means thetemperature corresponding to this peak.

On the supposition of polyethylene, the melting point is preferably 50to 140° C., more preferably 60 to 138° C., most preferably 70 to 135° C.In case where the melting point is lower than that range, the resin hasinsufficient heat resistance. In case where the melting point is higherthan that range, the resin shows poor adhesiveness.

[II] with Respect to Polar-Group-Containing Multinary Olefin Copolymer(B)

(1) Polar-Group-Containing Multinary Olefin Copolymer (B)

The polar-group-containing multinary olefin copolymer (B) according tothe invention is a multinary polar olefin copolymer (B) whichessentially includes three kinds of components derived from: one or morenonpolar monomers (X1) selected from ethylene and α-olefins having 3 to10 carbon atoms; one or more polar-group-containing monomers (Z1)selected from monomers having an epoxy group; and one or more othermonomers (Z2). Incidentally, polar-group-containing multinary olefincopolymers (B) obtained by copolymerizing monomers (X1), (Z1), and (Z2)by graft polymerization, high-pressure radical polymerization, or any ofthe other polymerization methods described above are already known.However, the copolymer (B) according to the invention is a randomcopolymer which, in contrast to such known polar-group-containingmultinary olefin copolymers, has been obtained by polymerization in thepresence of a transition metal and has the feature of having asubstantially linear molecular structure. In addition, this copolymer(B) satisfies the requirement of having a remarkable adhesion effect.This copolymer (B) hence differs considerably from the known copolymers.

(2) Nonpolar Monomers (X1)

Examples of the nonpolar monomers (X1) according to the inventioninclude ethylene and/or α-olefins having 3 to 10 carbon atoms.

Preferred examples thereof include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and4-methyl-1-pentene. Especially preferred examples thereof includeethylene. One α-olefin may be used, or two or more α-olefins may be usedin combination.

Examples of combinations of two include ethylene/propylene,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene,propylene/1-butene, propylene/1-hexene, and propylene/1-octene.

Examples of combinations of three include ethylene/propylene/1-butene,ethylene/propylene/1-hexene, ethylene/propylene/1-octene,propylene/1-butene/hexene, and propylene/1-butene/1-octene.

(3) Polar-Group-Containing Monomers (Z1) Containing Epoxy Group

The polar-group-containing monomers (Z1) according to the invention needto contain an epoxy group. So long as the olefin copolymer has epoxygroups, this copolymer can be laminated and bonded to bases made ofhighly polar thermoplastic resins, such as polyamide resins, polyesterresins, ethylene/vinyl alcohol copolymers (EVOH), and bondablefluororesins, and of metallic materials such as aluminum and steel.

As the polar-group-containing monomers containing an epoxy group, usecan be suitably made of those shown above as examples with regard to thepolar-group-containing olefin copolymer (A) described above.

(4) Other Monomers (Z2)

As the other monomers (Z2), which are a third component, any desiredmonomers which are identical with neither (X1) nor (Z1) can be used. Forexample, in the case where ethylene was selected as (X1), ethylenecannot be used as (Z2), but other α-olefins such as, for example,1-butene and 1-hexene are usable. Similarly, in the case where4-hydroxybutyl acrylate glycidylether was selected as (Z1), any monomerwhich is not 4-hydroxybutyl acrylate glycidylether can be used, such as,for example, an epoxy-group-containing monomer other than 4-hydroxybutylacrylate glycidylether or an acid-anhydride-containing monomer.

The other monomers (Z2) are compounds which each essentially contain acarbon-carbon double bond in the molecule and which may have asubstituent (polar group) containing an atom having an electronegativitydifferent from that of the carbon atom but need to have the substituent.

Examples of the polar group include halogens, hydroxy group (—OH),carboxyl group (—COOH), formyl group (—CHO), alkoxy groups (—OR), estergroups (—COOR), nitrile group (—CN), ether group (—O—), carbonyl group(═CO), epoxy group, and acid anhydride groups.

The other monomers (Z2) according to the invention are classified intonon-cyclic monomers or cyclic monomers by the position of thecarbon-carbon double bond in the molecule. Incidentally, the non-cyclicmonomers each may have a cyclic structure in the molecule so long as thecarbon-carbon double bond is located in the non-cyclic portion of themolecule.

(4-1) Non-Cyclic Monomers

Examples of the non-cyclic monomers include α-olefins, unsaturatedcarboxylic acids, unsaturated carboxylic acid anhydrides (in the casewhere the carbon-carbon double bond is not in a circle), and(meth)acrylic acid esters.

The α-olefins according to the invention are α-olefins having 3 to 20carbon atoms and are represented by the structural formula CH₂═CHR¹⁸. Inthe formula, R¹⁸ is a hydrogen atom or a hydrocarbon group having 1-18carbon atoms. R¹⁸ may be linear, branched, or cyclic and may have anunsaturated bond. R¹⁸ may contain a heteroatom at any position therein.Preferred examples among such α-olefins include α-olefins in which R¹⁸is a hydrogen atom or has 1-10 carbon atoms.

Specific compounds as examples of the α-olefins include ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexene,1,2-epoxy-4-vinylcyclohexene, styrene, 6-hydroxy-1-hexene,8-hydroxy-1-octene, 9,10-oxy-1-decene, 7-(N,N-dimethylamino)-1-heptene,3-triethoxysilyl-1-propene, ally alcohol, 2-allyloxyethanol, and allyacetate.

Examples of the unsaturated carboxylic acids include methacrylic acid,maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylicacid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid.

Examples of the unsaturated carboxylic acid anhydrides (in the casewhere the carbon-carbon double bond is not in a circle) include itaconicanhydride and 2,7-octadien-1-ylsuccinic anhydride.

The (meth)acrylic acid esters according to the invention are compoundsrepresented by the structural formula CH₂═C(R²¹)CO₂(R²²). In theformula, R²¹ is a hydrogen atom or a hydrocarbon group having 1-10carbon atoms, may be linear, branched, or cyclic, and may have anunsaturated bond. R²² is a hydrocarbon group having 1 to 30 carbonatoms, may be linear, branched, or cyclic, and may have an unsaturatedbond. Furthermore, R²² may contain a heteroatom at any position therein.

Preferred examples of the (meth)acrylic acid esters include(meth)acrylic acid esters in which R²¹ is a hydrogen atom or ahydrocarbon group having 1 to 5 carbon atoms. More preferred examplesthereof include acrylic acid esters in which R²¹ is a hydrogen atom ormethacrylic acid esters in which R²¹ is methyl.

Specific examples of the (meth)acrylic esters includemethyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate,isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate,t-butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate,cyclohexyl(meth)acrylate, octyl(meth)acrylate,2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate,dodecyl(meth)acrylate, phenyl(meth)acrylate, toluyl(meth)acrylate,benzyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxybutyl(meth)acrylate, 1,4-cyclohexanedimethanolmono(meth)acrylate, 4-hydroxybutyl(meth)acrylate glycidyl ether(4-HBAGE), 2-methoxyethyl(meth)acrylate, 3-methoxypropyl(meth)acrylate,glycidyl(meth)acrylate, (meth)acrylic acid ethylene oxide,trifluoromethyl(meth)acrylate, 2-trifluoromethylethyl(meth)acrylate, andperfluoroethyl(meth)acrylate.

One (meth)acrylic acid ester may be used, or a plurality of(meth)acrylic acid esters may be used in combination.

Preferred compounds include methyl acrylate, ethyl acrylate, n-butylacrylate, t-butyl acrylate, and 4-hydroxybutyl acrylate glycidyl ether.

(4-2) Cyclic Monomers

Examples of the cyclic monomers include norbornene-based olefins andunsaturated carboxylic acid anhydrides (in the case where thecarbon-carbon double bond is in a circle). Examples thereof furtherinclude compounds having the framework of a cycloolefin, such ascyclopentene, cyclohexene, norbornene, and ethylidenenorbornene, andderivative thereof which are compounds having a hydroxy group, alkoxidegroup, carboxylic acid group, ester group, aldehyde group, acidanhydride group, or epoxy group.

Examples of the unsaturated carboxylic acid anhydrides (in the casewhere the carbon-carbon double bond is in a circle) include maleicanhydride, citraconic anhydride, tetrahydrophthalic anhydride,5-norbornene-2,3-dicarboxylic acid anhydride,3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, andtetracyclo[6.2.1.13,6.02,7]dodeca-9-ene-4,5-dicarboxylic acid anhydride.

Examples of the norbornene-based olefins include the compoundrepresented by the following structural formula (E) or structuralformula (F). Structural formula (E) is norbornene having an acidanhydride group (a product of the Diels-Alder reaction ofcyclopentadiene with maleic anhydride, i.e.,5-norbornene-2,3-dicarboxylic acid anhydride), and structural formula(F) is norbornene having a hydroxy group.

(5) Amounts of Structural Units of Monomers (X1), (Z1), and (Z2)

The polar-group-containing multinary olefin copolymer (B) according tothe invention needs to include the units of monomers of three kinds intotal, which include one or more monomers (X1), one or more monomers(Z1), and one or more monomers (Z2).

The amount of the structural unit of (X1) is 80.000 to 99.998 mol %,preferably 80.000 to 99.98 mol %, more preferably 80.000 to 99.94 mol %.The amount of the structural unit of (Z1) is 0.001 to 19.999 mol %,preferably 0.01 to 15.000 mol %, more preferably 0.02 to 10.000 mol %,even more preferably 0.02 to 5.000 mol %. The amount of the structuralunit of (Z2) is 0.001 to 19.999 mol %, preferably 0.01 to 15.000 mol %,more preferably 0.02 to 10.000 mol %, even more preferably 0.02 to 5.000mol %. (X1)+(Z1)+(Z2) must be 100 mol %.

In the multinary olefin copolymer (B) according to the invention, thecrystallinity of the copolymer is determined by the contents of themonomers other than ethylene in cases when the polymerization wasconducted in the presence of a transition metal catalyst and whenethylene was selected as (X1). For example, in the case of a copolymerof ethylene with (Z1), the content of (Z1) is a factor which stronglyaffects the crystallinity of the copolymer.

Meanwhile, in the course of investigations which led to the presentinvention, the inventors discovered a factor that affects adhesiveness,besides the content of (Z1) in the copolymer. Namely, the inventorsdiscovered that a copolymer having a lower melting point shows higheradhesiveness. Specifically, the inventors showed that for furtherheightening adhesiveness, it is important that the copolymer shouldcontain (Z1) in an amount of 0.001 mol % or larger and that anothermonomer (Z2) should be introduced to thereby lower the melting point ofthe copolymer. The main purpose of copolymerizing monomer (Z2) inproducing the copolymer is to control the melting point of thecopolymer, and monomer (Z2) is not limited because of this. In addition,monomer (Z1) is frequently expensive as compared with monomer (X1) andmonomer (Z2). According to the invention, a minimum amount of monomer(Z1) which is necessary for heightening adhesiveness may be determinedfirst and the adhesiveness of the copolymer to be produced can befurther heightened by further copolymerizing monomer (Z2) in anappropriate amount.

The reason why copolymers having a lower melting point and higherflexibility have higher adhesiveness is not clear. However, it isprobably presumed that when a peel test such as those shown in JISK6854, 1-4 (1999) “Adhesives—Peel Adhesion Strength Test Methods” isconducted, flexible adhesives themselves show a larger deformation andthe magnitude of this deformation is measured as stress, resulting inhigh adhesiveness.

Furthermore, since the melting point of the copolymer according to theinvention can be regulated at will without changing the content of polargroups derived from monomer (Z1), the invention can attain both theadhesiveness and mechanical properties, in particular, impactresistance, of the copolymer.

(6) Structural Units of Polar-Group-Containing Olefin Copolymer (B)

The structural units of the polar-group-containing multinary olefincopolymer (B) according to the invention and the amounts of thestructural units are explained.

The structure derived from one molecule of ethylene and/or an α-olefinhaving 3 to 10 carbon atoms (X1), the structure derived from onemolecule of an epoxy-group-containing monomer (Z1), and the structurederived from one molecule of another monomer (Z2) are each defined asone structural unit within the polar-group-containing olefin copolymer(B). The proportion, in terms of mol %, of each structural unit in thepolar-group-containing olefin copolymer (B) is the amount of thestructural unit.

(7) Amount of Structural Unit of Epoxy-Group-Containing Monomer (Z1)

The amount of the structural unit of (Z1) according to the invention isselected from the range of usually 0.001 to 19.999 mol %, preferably0.01 to 15.000 mol %, more preferably 0.02 to 10.000 mol %, especiallypreferably 0.02 to 5.000 mol %. It is preferable that such structuralunits should be always present in the copolymer according to theinvention. In case where the amount of structural units derived from thepolar-group-containing monomer is less than that range, the adhesivenessto highly polar materials of different kinds is insufficient. In casewhere the amount thereof is larger than that range, sufficientmechanical properties are not obtained. One polar-group-containingmonomer may be used alone, or two or more polar-group-containingmonomers may be used in combination. The amount of the structural unitof each monomer can be determined by the method employing ¹H-NMRdescribed above.

(8) Weight-Average Molecular Weight (Mw) and Molecular-WeightDistribution Parameter (Mw/Mn) of Polar-Group-Containing MultinaryOlefin Copolymer (B)

It is desirable that the weight-average molecular weight (Mw) of thepolar-group-containing multinary olefin copolymer (B) according to theinvention should be in the range of usually 1,000 to 2,000,000,preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000,000,even more preferably 31,000 to 8000,000, especially preferably 33,000 to800,000. In case where the Mw thereof is less than 1,000, this copolymeris insufficient in properties such as mechanical strength and impactresistance. In case where the Mw thereof exceeds 2,000,000, thiscopolymer has exceedingly high melt viscosity and is difficult to mold.

It is desirable that the ratio of weight-average molecular weight (Mw)to number-average molecular weight (Mn), Mw/Mn, of thepolar-group-containing multinary olefin copolymer (B) according to theinvention should be in the range of usually 1.5 to 3.5, preferably 1.6to 3.3, more preferably 1.7 to 3.0. In case where the Mw/Mn thereof isless than 1.5, this copolymer is insufficient in suitability for variouskinds of processing, including laminating. In case where the Mw/Mnthereof exceeds 3.5, this copolymer shows poor adhesion strength. Thereare cases where Mw/Mn is referred to as molecular-weight distributionparameter.

(9) Melting Point

The multinary olefin copolymer (B) according to the invention needs tosatisfy the following relationship between the melting point Tm (° C.)thereof and the content of the polar-group-containing monomer [Z1]therein.

60<Tm<128−6.0[Z1]

It was discovered that factors which affect the adhesiveness of acopolymer include not only the (Z1) content of the copolymer but alsothe melting point of the copolymer, which considerably affects theadhesiveness, and that copolymers having a lower melting point showhigher adhesiveness. However, as a result of investigations made by thepresent inventors, it was discovered that in the case of, for example,an ethylene/(Z1) binary copolymer, for which ethylene was selected as(X1), the melting point of this copolymer depends on the content of (Z1)and it is extremely difficult to lower the melting point thereof tobelow 128−6.0[Z1] (° C.). There have hence been limitations in improvingthe adhesiveness.

Because of this, in case where the melting point of the copolymeraccording to the invention exceeds 128−6.0[Z1], an improvement inadhesiveness cannot be expected and sufficient adhesiveness is notimparted thereto. Meanwhile, in case where the melting point thereof islower than 60° C., this ethylene-based copolymer cannot retain theminimum heat resistance required.

(10) Molecular Structure of Polar-Group-Containing Multinary OlefinCopolymer (B)

The polar-group-containing olefin copolymer (B) according to theinvention is a random copolymer of (X1), (Z1), and (Z2).

The polar-group-containing multinary olefin copolymer (B) according tothe invention is characterized by being produced in the presence of atransition metal catalyst, and the molecular structure thereof islinear.

[III] with Respect to Production of Polar-Group-Containing OlefinCopolymer (A), Polar-Group-Containing Olefin Copolymer (A′), andPolar-Group-Containing Multinary Olefin Copolymer (B)

The polar-group-containing olefin copolymer (A), polar-group-containingolefin copolymer (A′), and polar-group-containing multinary olefincopolymer (B) according to the invention are obtained by suitablycopolymerizing the monomers using a transition metal catalyst.

(1) Polymerization Catalyst for Polar-Group-Containing Olefin Copolymer(A), Polar-Group-Containing Olefin Copolymer (A′), andPolar-Group-Containing Multinary Olefin Copolymer (B)

The kind of the polymerization catalyst to be used for producing thepolar-group-containing olefin copolymer (A), polar-group-containingolefin copolymer (A′), and polar-group-containing multinary olefincopolymer (B) according to the invention is not particularly limited solong as ethylene and/or one or more α-olefins having 3 to 20 carbonatoms can be copolymerized with one or more epoxy-group-containingmonomers using the catalyst. Examples thereof include compounds of aGroup-5 to Group-11 transition metal which has a chelatable ligand.

Preferred examples of the transition metal include a vanadium atom,niobium atom, tantalum atom, chromium atom, molybdenum atom, tungstenatom, manganese atom, iron atom, platinum atom, ruthenium atom, cobaltatom, rhodium atom, nickel atom, palladium atom, and copper atom.

Preferred of these are a vanadium atom, iron atom, platinum atom, cobaltatom, nickel atom, palladium atom, and rhodium atom. Especiallypreferred are a platinum atom, cobalt atom, nickel atom, and palladiumatom. One of these metals may be used alone, or two or more thereof maybe used in combination.

From the standpoint of activity in polymerization, it is preferable thatthe transition metal M of the transition metal catalyst according to theinvention should be an element selected from the group consisting ofnickel(II), palladium(II), platinum(II), cobalt(II), and rhodium(III),in particular, any of the Group-10 elements. Especially from thestandpoints of cost, etc., nickel(II) is preferred. The chelatableligand includes a ligand which has at least two atoms selected from thegroup consisting of P, N, O, and S and which is bidentate ormultidentate. The chelatable ligand is electronically neutral oranionic. Examples of the structure thereof are shown in a survey made byBrookhart, et al. (Chem. Rev., 2000, 100, 1169).

Preferred examples of bidentate anionic P,O ligands include phosphorussulfonic acids, phosphorus carboxylic acids, phosphorus phenols, andphosphorus enolates. Furthermore, examples of bidentate anionic N,Oligands include salicylaldiminates and pyridinecarboxylic acid. Otherexamples include diimine ligands, diphenoxide ligands, and diamideligands.

The structures of metal complexes obtained from chelatable ligands arerepresented by the following structural formula (A) and/or (B), to whichan arylphosphine compound, arylarsine compound, or arylantimony compoundthat may have one or more substituents has coordinated.

(In structural formulae (A) and (B), M represents a transition metalbelonging to any of Group 5 to Group 11 of the periodic table ofelements, i.e., the transition metal described above. X¹ representsoxygen, sulfur, —SO₃—, or —CO₂—. Y¹ represents carbon or silicon. Symboln represents an integer of 0 or 1. E¹ represents phosphorus, arsenic, orantimony. R³ and R⁴ each independently represent hydrogen or ahydrocarbon group which has 1 to 30 carbon atoms and may contain aheteroatom. The R⁵ moieties each independently represent hydrogen, ahalogen, or a hydrocarbon group which has 1 to 30 carbon atoms and maycontain a heteroatom. R⁶ and R⁷ each independently represent a hydrogenatom, a halogen atom, a hydrocarbon group which has 1 to 30 carbon atomsand may contain a heteroatom, OR², CO₂R², CO₂M′, C(O)N(R¹)₂, C(O)R²,SR², SO₂R², SOR², OSO₂R², P(O)(OR²)_(2-y)(R¹)_(y), CN, NHR², N(R²)₂,Si(OR¹)_(3-x)(R¹)_(x), OSi(OR¹)_(3-x)(R¹)_(x), NO₂, SO₃M′, PO₃M′₂,P(O)(OR₂)₂M′, or an epoxy-containing group. M′ represents an alkalimetal, an alkaline earth metal, ammonium, quaternary ammonium, orphosphonium; x represents an integer of 0 to 3; and y represents aninteger of 0 to 2. Incidentally, R⁶ and R⁷ may be linked to each otherto form an alicyclic ring, an aromatic ring, or a heterocycle containinga heteroatom selected from oxygen, nitrogen, and sulfur. These ringseach are a 5- to 8-membered ring, which may have one or moresubstituents thereon but need not have a substituent. R¹ representshydrogen or a hydrocarbon group having 1 to 20 carbon atoms. R²represents a hydrocarbon group having 1 to 20 carbon atoms. L¹represents a ligand coordinated to the M. R³ and L¹ may be bonded toeach other to form a ring.) More preferred is a transition metal complexrepresented by the following structural formula (C).

(In structural formula (C), M represents a transition metal belonging toany of Group 5 to Group 11 of the periodic table of elements, i.e., thetransition metal described above. X¹ represents oxygen, sulfur, —SO₃—,or —CO₂—. Y¹ represents carbon or silicon. Symbol n represents aninteger of 0 or 1. E¹ represents phosphorus, arsenic, or antimony. R³and R⁴ each independently represent hydrogen or a hydrocarbon groupwhich has 1 to 30 carbon atoms and may contain a heteroatom. The R⁵moieties each independently represent hydrogen, a halogen, or ahydrocarbon group which has 1 to 30 carbon atoms and may contain aheteroatom. R⁸, R⁹, R¹⁰, and R¹¹ each independently represent a hydrogenatom, a halogen atom, a hydrocarbon group which has 1 to 30 carbon atomsand may contain a heteroatom, OR², CO₂R², CO₂M′, C(O)N(R¹)₂, C(O)R²,SR², SO₂R², SOR², OSO₂R², P(O)(OR²)_(2-y)(R¹)_(y), CN, NHR², N(R²)₂,Si(OR¹)_(3-x)(R¹)_(x), OSi(OR¹)_(3-x)(R¹)_(x), NO₂, SO₃M′, PO₃M′₂,P(O)(OR²)₂M′, or an epoxy-containing group. M′ represents an alkalimetal, an alkaline earth metal, ammonium, quaternary ammonium, orphosphonium; x represents an integer of 0 to 3; and y represents aninteger of 0 to 2. Incidentally, two or more groups suitably selectedfrom R⁸ to R¹¹ may be linked to each other to form an alicyclic ring, anaromatic ring, or a heterocycle containing a heteroatom selected fromoxygen, nitrogen, and sulfur. These rings each are a 5- to 8-memberedring, which may have one or more substituents thereon but need not havea substituent. R¹ represents hydrogen or a hydrocarbon group having 1 to20 carbon atoms. R² represents a hydrocarbon group having 1 to 20 carbonatoms. L¹ represents a ligand coordinated to the M. R³ and L¹ may bebonded to each other to form a ring.)

Representative known examples of the catalyst including a Group-5 toGroup-11 transition metal compound having a chelatable ligand arecatalysts of the so-called SHOP type and Drent type. The SHOP typecatalyst is a catalyst including nickel metal and, coordinated thereto,a phosphorus-based ligand having an aryl group which may have asubstituent (see, for example, International Publication WO2010/050256). The Drent type catalyst is a catalyst including palladiummetal and, coordinated thereto, a phosphorus-based ligand having an arylgroup which may have a substituent (see, for example, JP-A-2010-202647).

(2) Organometallic Compound

When the polar-group-containing olefin copolymer (A),polar-group-containing olefin copolymer (A′), or polar-group-containingmultinary olefin copolymer (B) according to the invention is produced,the activity in polymerization can be further heightened by a method inwhich an epoxy-group-containing monomer is brought into contact with asmall amount of an organometallic compound and, thereafter, ethyleneand/or an α-olefin having 3 to 20 carbon atoms is copolymerized with theepoxy-group-containing monomer in the presence of the transition metalcatalyst.

The organometallic compound is an organometallic compound including oneor more hydrocarbon groups which may have a substituent, and can berepresented by the following structural formula (H).

R³⁰ _(n)M30X30_(m-n)  structural formula (H)

(In the formula, R³⁰ represents a hydrocarbon group which has 1 to 12carbon atoms and may have a substituent; M30 is a metal selected fromthe group consisting of Group-1, Group-2, Group-12, and Group-13elements of the periodic table; X30 represents a halogen atom or ahydrogen atom; m indicates the valence of the M30; and n is 1 to m.)

Examples of the organometallic compound represented by structuralformula (H) include alkylaluminums such as tri-n-butylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum andalkylaluminum halides such as methylaluminum dichloride, ethylaluminumdichloride, dimethylaluminum chloride, diethylaluminum chloride, anddiethylaluminum ethoxide. It is preferred to select a trialkylaluminum.It is more preferred to select a trialkylaluminum having hydrocarbongroups having 4 or more carbon atoms. It is even more preferred toselect a trialkylaluminum having hydrocarbon groups having 6 or morecarbon atoms. It is especially preferred to select tri-n-hexylaluminum,tri-n-octylaluminum, or tri-n-decylaluminum. Most suitable istri-n-octylaluminum.

From the standpoints of activity in polymerization and cost, it ispreferable that the organometallic compound should be contacted in suchan amount that the molar ratio thereof to the polar-group-containingcomonomer is from 10⁻⁵ to 0.9, preferably from 10⁻⁴ to 0.2, morepreferably from 10⁻⁴ to 0.1.

(2-1) Amount of Residual Aluminum (Al)

The amount of the aluminum (Al) remaining in 1 g of each of thepolar-group-containing olefin copolymer (A), polar-group-containingolefin copolymer (A′), and polar-group-containing multinary olefincopolymer (B) according to the invention is desirably 100,000 μg_(Al)/gor less, more desirably 70,000 μg_(Al)/g or less, even more desirably20,000 μg_(Al)/g or less, especially desirably 10,000 μg_(Al)/g or less,preferably 5,000 μg_(Al)/g or less, more preferably 1,000 μg_(Al)/g orless, most preferably 500 μg_(Al)/g or less. In case where the amountthereof is larger than that, the results are a decrease in mechanicalproperty, accelerated discoloration or deterioration of thepolymerization product, etc. The amount of residual aluminum (Al) ispreferably as small as possible. For example, the amount thereof may beas extremely small as about 1 μg_(Al)/g, or may be 0 μg_(Al)/g.Incidentally, the unit μg_(Al)/g means the amount, in μg, of aluminum(Al) contained in 1 g of the polar-group-containing olefin copolymer.

(2-2) Amount of Aluminum (Al)

The amount of the aluminum (Al) contained in the polar-group-containingolefin copolymer (A), polar-group-containing olefin copolymer (A′), orpolar-group-containing multinary olefin copolymer (B) according to theinvention can be calculated as the value obtained by dividing the amountof the aluminum contained in the alkylaluminum which was subjected tothe polymerization by the amount of the polar-group-containing olefincopolymer obtained.

The amount of the aluminum (Al) contained in the polar-group-containingolefin copolymer (A), polar-group-containing olefin copolymer (A′), orpolar-group-containing multinary olefin copolymer (B) is calculatedabove from the amount of the alkylaluminum which was supplied for thepolymerization. However, the amount thereof may be determined byfluorescent X-ray analysis or inductively coupled plasma (ICP) analysis.In the case of using fluorescent X-ray analysis or ICP analysis, ameasurement can be made, for example, by the following method.

<1> Fluorescent X-Ray Analysis

A 3 to 10 g portion of a test specimen is weighed and molded withheating and pressing by means of a hot press to produce a platy samplehaving a diameter of 45 mm. An examination is made on a central areahaving a diameter of 30 mm of the platy sample, using a scanningfluorescent X-ray analyzer “ZSX100e” (Rh tube, 4.0 kW), manufactured byRigaku Industrial Corp., under the following conditions.

X-ray output: 50 kV-50 mA

Analyzing crystal: PET

Detector: PC (proportional counter)

Detection line: Al—Kα line

The content of aluminum can be determined from a calibration curveproduced beforehand and from the results of the examination made underthose conditions. The calibration curve can be produced by examining aplurality of polyethylene resins for aluminum content by ICP analysisand further examining these polyethylene resins by fluorescent X-rayanalysis under those conditions.

<2> Inductively Coupled Plasma (ICP) Analysis

A test specimen, 3 mL of special-grade nitric acid, and 1 mL of anaqueous hydrogen peroxide solution (hydrogen peroxide content, 30% byweight) are introduced into a vessel made of Teflon (registeredtrademark), and a thermal decomposing operation is conducted using amicrowave decomposer (MLS-1200MEGA, manufactured by Milestone GeneralK.K.) at a maximum output of 500 W to obtain a solution of the testspecimen. The test specimen solution is examined with an ICPspectrometer (IRIS-AP, manufactured by Thermo Jarrell Ash Corp.). Thealuminum content can be thus determined. For determining the aluminumcontent, use is made of a calibration curve produced using standardsolutions having known aluminum element concentrations.

(3) Polymerization Methods for Producing Polar-Group-Containing OlefinCopolymer (A), Polar-Group-Containing Olefin Copolymer (A′), andPolar-Group-Containing Multinary Olefin Copolymer (B)

Polymerization methods for producing the polar-group-containing olefincopolymer (A), polar-group-containing olefin copolymer (A′), andpolar-group-containing multinary olefin copolymer (B) according to theinvention are not limited. It is preferred to use slurry polymerizationin which at least some of the yielded polymer forms a slurry in themedium, bulk polymerization in which the monomers themselves which havebeen liquefied are used as a medium, gas-phase polymerization in whichthe polymerization is conducted in vaporized monomers, high-pressureionic polymerization in which at least some of the yielded polymerdissolves in the monomers which have been liquefied at a hightemperature and a high pressure, or the like. With respect to the modeof polymerization, any of batch polymerization, semi-batchpolymerization, and continuous polymerization may be used. Furthermore,the polymerization may be living polymerization or may be one in whichthe monomers are polymerized while causing chain transfers. Moreover,chain shuttling reaction or coordinative chain transfer polymerization(CCTP) may be conducted using a so-called chain shuttling agent (CSA).Specific production processes and conditions are disclosed, for example,in JP-A-2010-260913 and JP-A-2010-202647.

[IV] Olefin-Based Resin Composition (D) (1) With Respect to Olefin-BasedResin Composition (D)

The olefin-based resin composition (D) according to the invention is acomposition obtained by incorporating 1 to 99,900 parts by weight of anolefin-based resin (C) into 100 parts by weight of apolar-group-containing olefin copolymer (A′). The amount of theolefin-based resin (C) to be incorporated is preferably 1 to 99,000parts by weight, more preferably 1 to 90,000 parts by weight, even morepreferably 1 to 50,000 parts by weight, especially preferably 1 to19,900 parts by weight. In case where the amount of the olefin-basedresin (C) incorporated is less than 1 part by weight or is larger than99,900 parts by weight, the olefin-based resin composition (D) showspoor adhesiveness.

In case where the polar-group-containing olefin copolymer (A′) in theolefin-based resin composition (D) is a polar-group-containing olefincopolymer produced by a high-pressure radical process, the adhesivenessdecreases drastically when an olefin-based resin (C) is incorporatedthereinto even in a small amount. In contrast, so long as thepolar-group-containing olefin copolymer in the olefin-based resincomposition is a polar-group-containing olefin copolymer (A′) accordingto the invention, the composition retains sufficient adhesiveness evenwhen the proportion of the olefin-based resin (C) incorporated thereintois high.

One polar-group-containing olefin copolymer (A′) or two or morepolar-group-containing olefin copolymers (A′) may be contained in theolefin-based resin composition (D) according to the invention.Meanwhile, one olefin-based resin (C) or two or more olefin-based resins(C) may be used therein.

(2) Methods for Producing Olefin-Based Resin Composition (D)

The olefin-based resin composition (D) according to the invention can beproduced using known methods. For example, the composition can beproduced by: a method in which a polar-group-containing olefin copolymer(A), an olefin-based resin (C), and other ingredients, which are addedif desired, are melt-kneaded using a single-screw extruder, twin-screwextruder, kneader, Banbury mixer, reciprocating kneading machine (BUSSKNEADER), roll kneader, or the like; or a method in which apolar-group-containing olefin copolymer (A′), an olefin-based resin (C),and other ingredients, which are added if desired, are dissolved in anappropriate good solvent (e.g., a hydrocarbon solvent such as hexane,heptane, decane, cyclohexane, or xylene) and the solvent is thenremoved.

(3) Other Ingredients

Various modifiers for resins and other ingredients may be incorporatedinto the olefin-based resin composition (D) according to the inventionso long as the incorporation thereof does not depart from the spirit ofthe functions of the composition of the invention. Examples of suchingredients include butadiene-based rubbers, isobutylene rubbers,isoprene-based rubbers, natural rubber, nitrile rubbers, and petroleumresins. One of these ingredients may be added alone, or a mixturethereof may be added.

(4) Polar-Group-Containing Olefin Copolymer (A′)

The polar-group-containing olefin copolymer (A′) according to theinvention is a copolymer of ethylene and/or α-olefin having 3 to 20carbon atoms with at least one epoxy-group-containing monomer. Themolecular structure of the polar-group-containing olefin copolymer (A′)and processes for producing the copolymer are basically the same asthose for the polar-group-containing olefin copolymer (A) andpolar-group-containing multinary olefin copolymer (B) according to thefirst aspect and second aspect of the invention.

(5) Amount of Structural Unit of Polar-Group-Containing Monomer

The amount of structural units derived from a polar-group-containingmonomer in the polar-group-containing olefin copolymer (A′) according tothe invention is selected from the range of usually 20 to 0.001 mol %,preferably 15 to 0.01 mol %, more preferably 10 to 0.02 mol %,especially preferably 5 to 0.02 mol %. It is preferable that suchstructural units should be always present in the polar-group-containingolefin copolymer according to the invention. In case where the amount ofstructural units derived from a polar-group-containing monomer is lessthan that range, the adhesiveness to highly polar materials of differentkinds is insufficient. In case where the amount thereof is larger thanthat range, sufficient mechanical properties are not obtained. Onepolar-group-containing monomer may be used alone, or two or morepolar-group-containing monomers may be used in combination.

(6) Weight-Average Molecular Weight (Mw) of Polar-Group-ContainingOlefin Copolymer (A′)

It is desirable that the weight-average molecular weight (Mw) of thepolar-group-containing olefin copolymer (A′) according to the inventionshould be in the range of usually 1,000 to 2,000,000, preferably 10,000to 1,500,000, more preferably 20,000 to 1,000,000, even more preferably31,000 to 800,000, especially preferably 33,000 to 800,000. In casewhere the Mw thereof is less than 1,000, the composition is insufficientin properties such as mechanical strength and impact resistance and haspoor adhesiveness to highly polar materials of different kinds. In casewhere the Mw thereof exceeds 2,000,000, the composition has exceedinglyhigh melt viscosity and is difficult to mold.

(7) Olefin-Based Resin (C)

The olefin-based resin (C) according to the invention is notparticularly limited. The olefin-based resin (C) can be selected fromethylene homopolymers, homopolymers obtained by polymerizing a monomerselected from α-olefins having 3 to 20 carbon atoms, copolymers obtainedby copolymerizing two or more monomers selected from ethylene and/orα-olefins having 3 to 20 carbon atoms, and copolymers of ethylene and/orone or more monomers selected from α-olefins having 3 to 20 carbon atomswith one or more vinyl monomers containing a polar group, thesehomopolymers and copolymers being obtained by high-pressure radicalpolymerization, high-, medium-, and low-pressure processes in which aZiegler type, Phillips type, or single-site catalyst is used, and otherknown processes. Preferred of these are ethylene homopolymers,copolymers of ethylene with one or more α-olefins having 3 to 20 carbonatoms, and copolymers of ethylene with one or more vinyl monomerscontaining a polar group.

The homopolymers according to the invention are obtained by polymerizingethylene only or polymerizing only one monomer selected from α-olefinshaving 3 to 20 carbon atoms. More preferred homopolymers are ethylenehomopolymers, propylene homopolymers, 1-butene homopolymers, 1-hexenehomopolymers, 1-octene homopolymers, 1-dodecene homopolymers, and thelike. Even more preferred are ethylene homopolymers and propylenehomopolymers.

The olefin-based copolymers according to the invention are olefin-basedcopolymers which each are obtained by copolymerizing two or moremonomers selected from ethylene, α-olefins having 3 to 20 carbon atoms,cycloolefins, other vinyl monomers containing no polar group, and vinylmonomers containing a polar group and which include at least one monomerselected from ethylene or α-olefins having 3 to 20 carbon atoms. Twomonomers may be subjected to polymerization, or three or more monomersmay be subjected to polymerization. Preferred olefin-based copolymersare copolymers of ethylene with one or more α-olefins selected fromα-olefins having 3 to 20 carbon atoms and copolymers of ethylene withone or more cycloolefins selected from cycloolefins. More preferred arecopolymers of ethylene with one or more α-olefins selected frompropylene, 1-butene, 1-hexene, and 1-octene and copolymers of ethylenewith norbornene.

Examples of the cycloolefins according to the invention includemonocyclic olefins such as cyclohexene and cyclooctene, polycyclicolefins such as norbornene, norbornadiene, dicyclopentadiene,dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene,dihydrotricyclopentadiene, tetracyclopentadiene, anddihydrotetracyclopentadiene, and substituted olefins formed by bondingfunctional groups to these olefins. Preferred cycloolefins among theseinclude norbornene. Olefin-based copolymers in which norbornene has beencopolymerized generally have a main-chain framework having an alicyclicstructure and hence have low hygroscopicity. Furthermore, additionpolymers thereof are excellent also in terms of heat resistance.

The monomers containing no polar group according to the invention aremonomers which each have one or more carbon-carbon double bonds in themolecular structure and in which the molecule is configured of elementsthat are carbon and hydrogen.

Examples thereof, which exclude ethylene and the α-olefins shown above,include dienes, trienes, and aromatic vinyl monomers. Preferred arebutadiene, isoprene, styrene, vinylcyclohexane, and vinylnorbornene.

The monomers containing a polar group according to the invention are notlimited. For example, the monomers can be selected from (a) monomerscontaining a carboxylic acid group or acid anhydride group, (b) monomerscontaining an ester group, (c) monomers containing a hydroxyl group, (d)monomers containing an amino group, and (e) monomers containing a silanegroup.

Examples of the monomers (a) containing a carboxylic acid group or acidanhydride group include α,β-unsaturated dicarboxylic acids such asmaleic acid, fumaric acid, citraconic acid, and itaconic acid, theanhydrides of these acids, and unsaturated monocarboxylic acids such asacrylic acid, methacrylic acid, furoic acid, crotonic acid, vinylacetate, and pentenoic acid. Examples of the monomers (b) containing anester group include methyl(meth)acrylate, ethyl(meth)acrylate, (n- oriso-)propyl(meth)acrylate, and (n-, iso-, or tert-)butyl(meth)acrylate,and especially preferred examples thereof include methyl acrylate.Examples of the monomers (c) containing a hydroxyl group includehydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate. Examplesof the monomers (d) containing an amino group includeaminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,diethylaminoethyl(meth)acrylate, and cyclohexylaminoethyl(meth)acrylate.Examples of the monomers (e) containing a silane group includeunsaturated silane compounds such as vinyltrimethoxysilane,vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.

(8) Processes for Producing Olefin-Based Resin (C)

Processes for producing the olefin-based resin (C) according to theinvention are not limited. Examples thereof include a high-pressureradical polymerization process, high-, medium-, and low-pressureprocesses in which a Ziegler type, Phillips type, or single-sitecatalyst is used, and other known processes.

(9) Melt Flow Rate (MFR) of Olefin-Based Resin (C)

It is desirable that the MFR of the olefin-based resin (C), which ismeasured in accordance with JIS K7120 (1999), conditions D under theconditions of a temperature of 190° C. and a load of 2.16 kg, should bein the range of usually 0.01 to 100 g/10 min, preferably 0.1 to 80 g/10min, more preferably 0.3 to 50 g/10 min. In case where the MFR thereofexceeds 100 g/10 min, the composition is insufficient in properties suchas mechanical strength and impact resistance. In case where the MFRthereof is less than 0.01 g/10 min, the composition has exceedingly highmelt viscosity and is difficult to mold.

(10) Density of Olefin-Based Resin (C)

It is desirable that the density of the olefin-based resin (C), which isdetermined in accordance with JIS K7112, Method A (1999), should be inthe range of usually 0.840 to 1.20 g/cm³, preferably 0.850 to 0.990g/cm³, more preferably 0.860 to 0.980 g/cm³, especially preferably 0.870to 0.970 g/cm³. In case where the density thereof exceeds 1.20 g/cm³,the composition is insufficient in properties such as impact resistance.In case where the density thereof is less than 0.840 g/cm³, thecomposition has poor heat resistance.

[V] Olefin-Based Resin Composition (D′) (1) With Respect to Olefin-BasedResin Composition (D′)

The olefin-based resin composition (D′) is the olefin-based resincomposition (D) wherein the olefin-based resin (C) contained therein hasbeen further limited in the range of density and the range of meltingpoint. It has hence become possible to produce an olefin-based resincomposition having a satisfactory balance between sufficientadhesiveness to materials of different kinds and heat resistance.Namely, the olefin-based resin composition (D′) is basically identicalwith the olefin-based resin composition (D), except that the composition(D′) differs from the composition (D) in the ranges of the density andmelting point of the olefin-based resin (C) contained as a component.

(2) Density of Olefin-Based Resin (C) Contained in Olefin-Based ResinComposition (D′)

The density of the olefin-based resin (C) contained in the olefin-basedresin composition (D′), which is determined in accordance with JISK7112, Method A (1999), is preferably 0.890 to 1.20 g/cm³, morepreferably 0.895 to 0.990 g/cm³, even more preferably 0.900 to 0.980g/cm³. In case where the density thereof is less than that range, thecomposition has insufficient heat resistance. In case where the densitythereof is higher than that range, the composition has poor impactresistance.

(3) Melting Point of Olefin-Based Resin (C) Contained in Olefin-BasedResin Composition (D′)

The melting point of the olefin-based resin (C) contained in theolefin-based resin composition (D′) is expressed in terms of themaximum-peak temperature in an endothermic curve determined with adifferential scanning calorimeter (DSC).

The olefin-based resin (C) contained in the olefin-based resincomposition (D′) can be a crystalline resin or an amorphous resin.Although the melting point of the crystalline resin can be measured bythe method of melting point measurement described above, there are caseswhere the amorphous resin shows no melting point. Since thepolar-group-containing olefin copolymer (A′) according to the inventionis a crystalline resin, it is preferable that the olefin-based resin (C)should also have a melting point. However, so long as the olefin-basedresin composition (D′) has a melting point within a preferred range andshows adhesiveness, the olefin-based resin (C) may be an amorphousolefin-based resin. The melting point of the olefin-based resin (C)contained in the olefin-based resin composition (D′), the melting pointbeing measured by the method of melting point measurement describedabove, is preferably in the range of 90 to 170° C., more preferably inthe range of 100 to 155° C., especially preferably in the range of 110to 140° C. In case where the melting point thereof is lower than thatrange, the composition has insufficient heat resistance. In case wherethe melting point thereof is higher than that range, the compositionshows poor adhesiveness.

(4) Melting Point of Olefin-Based Resin Composition (D′)

The melting point of the olefin-based resin composition (D′) accordingto the invention is expressed in terms of the maximum-peak temperaturein an endothermic curve determined with a differential scanningcalorimeter (DSC).

The melting point of the olefin-based resin composition (D′) ispreferably 119 to 170° C., more preferably 119.5 to 155° C., mostpreferably 120 to 140° C. In case where the melting point thereof islower than that range, the composition has insufficient heat resistance.In case where the melting point thereof is higher than that range, thecomposition shows poor adhesiveness.

(5) Heat of Fusion ΔH of Olefin-Based Resin Composition (D′)

The heat of fusion ΔH of the olefin-based resin composition (D′)according to the invention is determined in accordance with JIS K7122(1987). Namely, the heat of fusion thereof is determined from the areaof the peak(s) appearing on an endothermic curve determined with adifferential scanning calorimeter (DSC). The heat of fusion ΔH thereofis preferably in the range of 80 to 300 J/g, more preferably in therange of 85 to 290 J/g, especially preferably in the range of 100 to 280J/g. In case where the heat of fusion thereof is less than that range,this composition has insufficient heat resistance. In case where theheat of fusion thereof is larger than that range, this composition showspoor adhesiveness.

[VI] Olefin-Based Resin Composition (D″) (1) With Respect toOlefin-Based Resin Composition (D″)

The olefin-based resin composition (D″) is the olefin-based resincomposition (D) wherein the olefin-based resin (C) contained therein hasbeen further limited in the range of density and the range of meltingpoint. As a result, the adhesiveness to materials of other kinds can bemarkedly improved and the epoxy group content in the olefin-based resincomposition can be reduced to a low value, thereby making it possible toavoid the crosslinking of molecular chains and gelation which are causedby the reaction between epoxy groups and to eliminate the fear that themechanical properties, impact resistance, moldability, etc. may beimpaired by the crosslinking or gelation. Namely, the olefin-based resincomposition (D″) is basically identical with the olefin-based resincomposition (D), except that the composition (D″) differs from thecomposition (D) in the ranges of the density and melting point of theolefin-based resin (C) contained as a component.

(2) Density of Olefin-Based Resin (C) Contained in Olefin-Based ResinComposition (D″)

The density of the olefin-based resin (C) according to the invention,which is determined in accordance with JIS K7112, Method A (1999), isdesirably 0.840 to 0.932 g/cm³, more desirably 0.840 to 0.928 g/cm³,even more desirably 0.840 to 0.922 g/cm³, preferably 0.840 to 0.915g/cm³, especially preferably 0.840 to 0.910 g/cm³. In case where thedensity thereof is higher than that range, the composition has pooradhesiveness. The more the olefin-based resin (C) contained in theolefin-based resin composition (D″) is flexible, that is, the lower thedensity of the resin (C), the more the adhesiveness is improved. Forthis reason, there is no particular lower limit. However, on thesupposition of polyethylene, it is difficult to produce an olefin-basedresin having a density lower than 0.840 g/cm³.

(3) Melting Point of Olefin-Based Resin (C) Contained in Olefin-BasedResin Composition (D″)

The melting point of the olefin-based resin (C) contained in theolefin-based resin composition (D″) is expressed in terms of themaximum-peak temperature in an endothermic curve determined with adifferential scanning calorimeter (DSC).

The melting point thereof is desirably 30 to 124° C., more desirably 30to 120° C., even more desirably 30 to 115° C., preferably 30 to 110° C.,especially preferably 30 to 100° C. In case where the melting pointthereof is higher than that range, the composition has pooradhesiveness. The more the olefin-based resin (C) contained in theolefin-based resin composition (D″) is flexible, that is, the lower themelting point of the resin (C), the more the adhesiveness is improved.For this reason, there is no particular lower limit. However, on thesupposition of polyethylene, it is difficult to produce an olefin-basedresin having a melting point lower than 30° C.

Meanwhile, the heat of fusion ΔH (J/g), which is calculated from thearea of the peak(s) appearing on an endothermic curve obtained by a DSCmeasurement, depends on the crystallinity of the olefin-based resin.Consequently, as the crystallinity of the olefin-based resin becomeslower, the ΔH decreases and it becomes difficult to observe a peak onthe endothermic curve. Namely, there are cases where olefin-based resinshaving a low crystallinity show no melting point defined by themaximum-peak temperature in an endothermic curve. Since to blend aflexible olefin-based resin is in the spirit of the invention, a resinwhich shows no melting point according to the definition may be used solong as the resin has a low crystallinity and is flexible. The heat offusion ΔH (J/g) is a value calculated from the area of the peak(s)appearing on an endothermic curve obtained in a DSC measurement whenheat flow (mW) and temperature (° C.) are plotted as ordinate andabscissa, respectively, and means the total amount of energy, in termsof J unit, which is absorbed when the crystals contained in 1 g of aspecimen melt.

[VII] Additives

Additives such as an antioxidant, ultraviolet absorber, lubricant,antistatic agent, colorant, pigment, crosslinking agent, blowing agent,nucleating agent, flame retardant, conductive material, and filler maybe incorporated into the polar-group-containing olefin copolymer (A),polar-group-containing multinary olefin copolymer (B), olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) according to the invention so longas the incorporation thereof does not depart from the spirit of theinvention.

[VIII] Adhesive

The polar-group-containing olefin copolymer (A), polar-group-containingmultinary olefin copolymer (B), olefin-based resin composition (D),olefin-based resin composition (D′), and olefin-based resin composition(D″) according to the invention show high adhesiveness to other basesand have made it possible to produce industrially useful layeredproducts. The superiority of the use thereof as adhesives has beendemonstrated by the data obtained in the Examples which will be givenlater and by comparisons between the Examples and the ComparativeExamples.

[IX] Layered Product and Composited Products (1) Materials for theLayered Product

The layered product according to the invention is a layered productwhich includes: a layer constituted of any of the polar-group-containingolefin copolymer (A), polar-group-containing multinary olefin copolymer(B), olefin-based resin composition (D), olefin-based resin composition(D′), and olefin-based resin composition (D″); and a base layer.Examples of the base include: films or sheets (including stretched orprinted films or sheets) of thermoplastic resins having film-formingability, such as polyethylene-based resins, e.g., high-densitypolyethylene, medium-density polyethylene, low-density polyethylene,ethylene/vinyl acetate copolymers, and ethylene/acrylic estercopolymers, polypropylene-based resins, e.g., ionomers, propylenehomopolymer resins, and copolymers of propylene with other α-olefin(s),olefin-based resins, e.g., poly(l-butene) and poly(4-methyl-1-pentene),vinyl-based polymers, e.g., poly(vinyl chloride), poly(vinylidenechloride), polystyrene, polyacrylates, and polyacrylonitrile,polyamide-based resins, e.g., nylon-6, nylon-66, nylon-10, nylon-11,nylon-12, nylon-610, and poly(m-xylylene-adipamide), polyester-basedresins, e.g., poly(ethylene terephthalate), poly(ethyleneterephthalate/isophthalate), poly(butylene terephthalate), poly(lacticacid), poly(butylene succinate), and aromatic polyesters, poly(vinylalcohol), ethylene/vinyl alcohol copolymers, polycarbonate resins,bondable fluororesins, thermosetting resins, e.g., phenolic resins,epoxy resins, urea resins, melamine resins, urea resins, alkyd resins,unsaturated polyesters, polyurethanes, and thermosetting polyimides, andcellulosic polymers, e.g., cellophane; foils or sheets of metals such asaluminum, iron, copper, or alloys including any of these metals as themain component; vapor-deposited films of inorganic oxide, such asplastic films with vapor-deposited silica and plastic films withvapor-deposited alumina; vapor-deposited films of, for example, a metalsuch as gold, silver, or aluminum or a compound, excluding the oxide, ofany of such metals; various kinds of paper such as wood-free paper,kraft paper, paper boards, glassine paper, and synthetic paper; andcellophane, woven fabric, and nonwoven fabric.

The base layer according to the invention can be suitably selected inaccordance with the intended use thereof or the kind of the object to bewrapped. For example, in the case where the object to be wrapped is aperishable food, use can be made of a resin which is excellent in termsof transparency, rigidity, and gas permeation resistance, such as apolyamide, poly(vinylidene chloride), ethylene/vinyl alcohol copolymer(EVOH), poly(vinyl alcohol), or polyester. In the case where the objectto be wrapped is a confection, fibers, or the like, it is preferred touse polypropylene or the like, which is satisfactory in terms oftransparency, rigidity, and water permeation resistance. In the case ofapplication to fuel tanks for motor vehicles or to tubes, hoses, pipes,or the like through which fuel passes, use can be made of a resin havingexcellent fuel impermeability, such as an EVOH, a polyamide, or afluororesin. Examples of barrier resins include polyamide-based resins,polyester-based resins, EVOH, poly(vinylidene chloride)-based resins,polycarbonate-based resins, oriented polypropylene (OPP), orientedpolyesters (OPET), oriented polyamides, films coated by vapor depositionof an inorganic metal oxide, such as films coated with vapor-depositedalumina and films coated with vapor-deposited silica, films coated byvapor deposition of a metal, such as films coated with vapor-depositedaluminum, and metal foils.

(2) Applications of the Layered Product

The layered product according to the invention is suitable for use as,for example, packaging materials for foods. Examples of the foodsinclude snack confections such as potato chips, confectionery includingbiscuits, rice crackers, and chocolates, powdery seasonings such aspowdered soup, and foods such as flakes of dried bonito and smokedfoods. A pouch container can be formed by disposing the layered productso that the surface of the layer of an ethylene-based copolymer faces toitself and heat-sealing at least some of the superposed edges.Specifically, such pouch containers are suitable for use, for example,for packaging aqueous matter and as general-purpose bags, liquid-souppackages, paper vessels for liquids, raw sheets for laminating,special-shape packaging bags for liquids (e.g., standing pouches),standardized bags, heavy-duty bags, semi-heavy-duty bags, wrappingfilms, sugar bags, packaging bags for oily matter, various packagingcontainers such as containers for food packaging, and transfusion bags.

(3) Production of the Layered Product

Examples of processing techniques for producing the layered productaccording to the invention include conventionally known techniques suchas ordinary press molding, extrusion molding techniques such asair-cooled inflation molding, inflation molding with two-stage aircooling, high-speed inflation molding, flat-die molding (T-die molding),and water-cooled inflation molding, laminating techniques such asextrusion laminating, sandwich laminating, and dry laminating, blowmolding, air-pressure forming, injection molding, and rotationalmolding.

(4) Laminate

The laminate according to the invention is a layered product which canbe produced by a known laminating technique such as, for example,extrusion laminating, sandwich laminating, or dry laminating. Thislaminate is a layered product which can be produced by laminating alaminating material with at least one base layer, the laminatingmaterial including any of the polar-group-containing olefin copolymer(A), polar-group-containing multinary olefin copolymer (B), olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) of the invention.

(5) Extrusion-Molded Article

The extrusion-molded article according to the invention is anextrusion-molded article obtained by molding any of thepolar-group-containing olefin copolymer (A), polar-group-containingmultinary olefin copolymer (B), olefin-based resin composition (D),olefin-based resin composition (D′), and olefin-based resin composition(D″) according to the invention by extrusion molding.

(6) Multilayered Coextrusion-Molded Article

The multilayered coextrusion-molded article according to the inventionis a multilayered coextrusion-molded article which can be molded byknown multilayer coextrusion molding, and which at least includes alayer including any of the polar-group-containing olefin copolymer (A),polar-group-containing multinary olefin copolymer (B), olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) of the invention.

(7) Multilayered Film

The multilayered film according to the invention is a multilayered filmwhich can be produced by a known technique for multilayered-filmmolding, and which at least includes a base layer and a layer thatincludes any of the polar-group-containing olefin copolymer (A),polar-group-containing multinary olefin copolymer (B), olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) of the invention.

(8) Multilayered Blow-Molded Article

The multilayered blow-molded article according to the invention is amultilayered blow-molded article which can be produced by knownmultilayer blow-molding, and which at least includes a base layer and alayer that includes any of the polar-group-containing olefin copolymer(A), polar-group-containing multinary olefin copolymer (B), olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) of the invention.

(9) Multilayered Tubular Molded Article

The multilayered tubular molded article according to the invention is amultilayered tubular molded article which can be produced by a knowntechnique for molding multilayered tubular objects, and which at leastincludes a base layer and a layer that includes any of thepolar-group-containing olefin copolymer (A), polar-group-containingmultinary olefin copolymer (B), olefin-based resin composition (D),olefin-based resin composition (D′), and olefin-based resin composition(D″) of the invention.

(10) Multilayered Sheet

The multilayered sheet according to the invention is a multilayeredsheet which can be produced by known multilayered-sheet molding, andwhich at least includes a base layer and a layer that includes any ofthe polar-group-containing olefin copolymer (A), polar-group-containingmultinary olefin copolymer (B), olefin-based resin composition (D),olefin-based resin composition (D′), and olefin-based resin composition(D″) of the invention.

(11) Injection-Molded Article

The injection-molded article according to the invention is aninjection-molded article obtained by molding any of thepolar-group-containing olefin copolymer (A), polar-group-containingmultinary olefin copolymer (B), olefin-based resin composition (D),olefin-based resin composition (D′), and olefin-based resin composition(D″) according to the invention by injection molding. For producing theinjection-molded article according to the invention, known techniquescan be used.

(12) Multilayered Injection-Molded Article

The multilayered injection-molded article according to the invention isa multilayered injection-molded article which at least includes a layerincluding any of the polar-group-containing olefin copolymer (A),polar-group-containing multinary olefin copolymer (B), olefin-basedresin composition (D), olefin-based resin composition (D′), andolefin-based resin composition (D″) of the invention and which can beproduced by superposing a plurality of layers using injection molding.The multilayered injection-molded article may have any configuration solong as two or more materials have been disposed in a multilayerarrangement. The multilayered injection-molded article according to theinvention can be molded by a known injection molding technique capableof multilayer injection molding.

(13) Coated Metallic Member

The coated metallic member according to the invention is a coatedmetallic member which can be produced by coating a metal with any of thepolar-group-containing olefin copolymer (A), polar-group-containingmultinary olefin copolymer (B), olefin-based resin composition (D),olefin-based resin composition (D′), and olefin-based resin composition(D″) as a metal-covering material.

EXAMPLES

The present invention will be explained below in detail by reference toExamples and Comparative Examples to demonstrate the rationality andpredominance of the configurations of the invention and the superioritythereof to prior-art techniques by means of preferred data obtained inthe Examples and comparisons between the Examples and the ComparativeExamples. The test methods used for examining properties ofpolar-group-containing olefin copolymers produced in the invention andthe test methods used for examining the layered products obtained are asfollows.

Experiment Example 1 Evaluation of Polar-Group-Containing OlefinCopolymers (1) Amount of Polar-Group-Containing Structural Units inPolar-Group-Containing Olefin Copolymer

The amount of polar-group-containing structural units in eachpolar-group-containing olefin copolymer was determined using a ¹H-NMRspectrum. A detailed explanation was given hereinabove.

(2) Weight-Average Molecular Weight (Mw) and Molecular-WeightDistribution Parameter (Mw/Mn)

Weight-average molecular weight (Mw) was determined by gel permeationchromatography (GPC). Molecular-weight distribution parameter (Mw/Mn)was determined by further determining the number-average molecularweight (Mn) by gel permeation chromatography (GPC) and calculating theratio between Mw and Mn, i.e., Mw/Mn. A detailed explanation was givenhereinabove.

(3) Melting Point

Melting point is expressed by the peak temperature in an endothermiccurve determined with a differential scanning calorimeter (DSC). A DSC(DSC 7020) manufactured by SII Nano Technology Inc. was used for themeasurement, which was conducted under the following conditions.

About 5.0 mg of a specimen was packed into an aluminum pan, and thecontents were heated to 200° C. at 10° C./min, held at 200° C. for 5minutes, and then cooled to 30° C. at 10° C./min. This specimen was heldat 30° C. for 5 minutes and then heated again at 10° C./min to obtain anendothermic curve for this heating. The maximum-peak temperature in thecurve was taken as the melting point.

(4) Adhesion Strength

Adhesion strength was measured by preparing both a test sample in apressed-plate form and various base films, stacking and hot-pressing thetest sample and each of the base films to thereby produce a layeredproduct, and subjecting the layered product to a peel test. The steps ofthe preparation methods and measuring method are explained in order.

[1] Method for Preparing Pressed Plate of Test Sample

A test sample was placed in a mold for hot pressing which had dimensionsof 50 mm×60 mm and a thickness of 0.5 mm. In a hot press having asurface temperature of 180° C., preheating was conducted for 5 minutesand pressurization and depressurization were repeated to thereby removethe gas remaining in the molten resin. Furthermore, the resin waspressed at 4.9 MPa and held for 5 minutes. Thereafter, the mold wastransferred to a press having a surface temperature of 25° C., and theresin was held for 3 minutes at a pressure of 4.9 MPa to thereby coolthe resin. Thus, a pressed plate having a thickness of about 0.5 mm wasproduced.

[2] Method for Preparing EVOH Film

A multilayer T-die molding machine was used to mold a two-kindthree-layer film composed of an EVOH as the central layer and LLDPE asboth outer layers. Thereafter, the LLDPE as the outer layers was peeledoff to thereby prepare an EVOH single-layer film having a thickness of100 μm. The film molding conditions are as follows.

Molding machine: two-kind three-layer T-die

Molding temperature: 200° C.

Layer configuration: LLDPE/EVOH/LLDPE

Film thickness: 300 μm (100 μm/100 μm/100 μm)

Outer layers: LLDPE (trade name: Novatec UF943, manufactured by JapanPolyethylene Corp.), MFR=2.0 g/10 min, density=0.937/cm³

Interlayer: EVOH (trade name: EVAL F101B, manufactured by Kuraray Co.Ltd.)

[3] Method for Preparing Polyamide Film

A multilayer T-die molding machine was used to mold a two-kindthree-layer film composed of a polyamide as the central layer and LLDPEas both outer layers. Thereafter, the LLDPE as the outer layers waspeeled off to thereby prepare a polyamide single-layer film having athickness of 100 μm. The film molding conditions are as follows.

Molding machine: two-kind three-layer T-die

Molding temperature: 250° C.

Layer configuration: LLDPE/EVOH/LLDPE

Film thickness: 300 μm (100 μm/100 μm/100 μm)

Outer layers: LLDPE (trade name: Novatec UF943, manufactured by JapanPolyethylene Corp.), MFR=2.0 g/10 min, density=0.937/cm³

Interlayer: polyamide (trade name: Amilan CM1021FS, manufactured byToray Industries, Inc.)

[4] Method for Producing Polyester Film

A multilayer T-die molding machine was used to mold a two-kindthree-layer film composed of a polyester as the central layer and LLDPEas both outer layers. Thereafter, the LLDPE as the outer layers waspeeled off to thereby prepare a polyester single-layer film having athickness of 100 μm. The film molding conditions are as follows.

Molding machine: two-kind three-layer T-die

Molding temperature: 250° C.

Layer configuration: LLDPE/EVOH/LLDPE

Film thickness: 300 μm (100 μm/100 μm/100 μm)

Outer layers: LLDPE (trade name: Novatec UF943, manufactured by JapanPolyethylene Corp.), MFR=2.0 g/10 min, density=0.937/cm³

Interlayer: poly(ethylene terephthalate) (trade name: Novapex IG229Z,manufactured by Mitsubishi Chemical Corp.)

[5] Method for Producing Fluororesin Film

A multilayer T-die molding machine was used to mold a two-kindthree-layer film composed of a fluororesin as the central layer andLLDPE as both outer layers. Thereafter, the LLDPE as the outer layerswas peeled off to thereby prepare a fluororesin single-layer film havinga thickness of 100 μm. The film molding conditions are as follows.

Molding machine: two-kind three-layer T-die

Molding temperature: 230° C.

Layer configuration: LLDPE/EVOH/LLDPE

Film thickness: 300 μm (100 μm/100 μm/100 μm)

Outer layers: LLDPE (trade name: Novatec UF943, manufactured by JapanPolyethylene Corp.), MFR=2.0 g/10 min, density=0.937/cm³

Interlayer: fluororesin (trade name: Neoflon EFEP RP-5000, manufacturedby Daikin Industries, Ltd.)

[6] Method for Preparing Layered Product of EVOH Film with Test Sample

The pressed plate of a test sample obtained by the Method for PreparingPressed Plate given above and the EVOH film which had been obtained bythe Method for Preparing EVOH Film given above and cut into dimensionsof 50 mm×60 mm were stacked and placed in a mold for hot pressing whichhad dimensions of 50 mm×60 mm and a thickness of 0.5 mm. Using a hotpress having a surface temperature of 200° C., the stack was pressed at4.9 MPa for 3 minutes. Thereafter, the mold was transferred to a presshaving a surface temperature of 25° C., and the work was held for 3minutes at a pressure of 4.9 MPa to thereby cool the work. Thus, alayered product of the pressed test-sample plate with the EVOH wasprepared.

[7] Method for Preparing Layered Product of Polyamide Film with TestSample

The pressed plate of a test sample obtained by the Method for PreparingPressed Plate given above and the polyamide film which had been obtainedby the Method for Preparing Polyamide Film given above and cut intodimensions of 50 mm×60 mm were stacked and placed in a mold for hotpressing which had dimensions of 50 mm×60 mm and a thickness of 0.5 mm.Using a hot press having a surface temperature of 250° C., the stack waspressed at 4.9 MPa for 5 minutes. Thereafter, the mold was transferredto a press having a surface temperature of 25° C., and the work was heldfor 3 minutes at a pressure of 4.9 MPa to thereby cool the work. Thus, alayered product of the pressed test-sample plate with the polyamide wasprepared.

[8] Method for Preparing Layered Product of Polyester Film with TestSample

The pressed plate of a test sample obtained by the Method for PreparingPressed Plate given above and the polyester film which had been obtainedby the Method for Preparing Polyester Film given above and cut intodimensions of 50 mm×60 mm were stacked and placed in a mold for hotpressing which had dimensions of 50 mm×60 mm and a thickness of 0.5 mm.Using a hot press having a surface temperature of 200° C., the stack waspressed at 4.9 MPa for 3 minutes. Thereafter, the mold was transferredto a press having a surface temperature of 25° C., and the work was heldfor 3 minutes at a pressure of 4.9 MPa to thereby cool the work. Thus, alayered product of the pressed test-sample plate with the polyester wasprepared.

[9] Method for Preparing Layered Product of Fluororesin Film with TestSample

The pressed plate of a test sample obtained by the Method for PreparingPressed Plate given above and the fluororesin film which had beenobtained by the Method for Preparing Fluororesin Film given above andcut into dimensions of 50 mm×60 mm were stacked and placed in a mold forhot pressing which had dimensions of 50 mm×60 mm and a thickness of 0.5mm. Using a hot press having a surface temperature of 200° C., the stackwas pressed at 4.9 MPa for 3 minutes. Thereafter, the mold wastransferred to a press having a surface temperature of 25° C., and thework was held for 3 minutes at a pressure of 4.9 MPa to thereby cool thework. Thus, a layered product of the pressed test-sample plate with thefluororesin was prepared.

[10] Method for Measuring Adhesion Strength of Layered Product

Each layered product obtained by the Method for Preparing LayeredProduct was cut into a width of 10 mm and subjected to T-peeling at aspeed of 50 mm/min using Tensilon (manufactured by Toyo Seiki Ltd.),thereby measuring the adhesion strength. The unit of the adhesionstrength is gf/10 mm. In cases when the adhesion strength is exceedinglyhigh, the test sample layer or the base layer yields and ruptures duringthe peel test. This is a phenomenon which occurs since the adhesionstrength of the layered product is higher than the lower of the tensilestrengths at rupture of the test sample layer and base layer; it can bedeemed that the adhesiveness thereof is exceedingly high. In the casewhere the adhesion strength was unable to be measured due to thephenomenon, this result is indicated by “peeling impossible” in thecolumn “Adhesion strength” for the Example; it is deemed that the testsample had been more highly bonded than those in layered products inwhich values of adhesion strength were measured.

(5) Chemical Resistance [1] Method for Preparing Pressed Plate of TestSample

A test sample was placed in a mold for hot pressing which had dimensionsof 50 mm×60 mm and a thickness of 1 mm. In a hot press having a surfacetemperature of 180° C., preheating was conducted for 5 minutes andpressurization and depressurization were repeated to thereby remove thegas remaining in the molten resin. Furthermore, the resin was pressed at4.9 MPa and held for 5 minutes. Thereafter, the mold was transferred toa press having a surface temperature of 25° C., and the resin was heldfor 3 minutes at a pressure of 4.9 MPa to thereby cool the resin. Thus,a pressed test-sample plate having a thickness of about 0.9 mm wasproduced.

[2] Method for Evaluating Chemical Resistance

The pressed test-sample plate prepared by the Method for PreparingPressed Plate of Test Sample was cut into a width of 10 mm to produce atest piece for chemical-resistance evaluation. This test piece forevaluation was placed in a pressure vessel, and a three-chemical mixturesolution obtained by mixing 455 mL of isooctane, 455 mL of toluene, and90 mL of ethanol was added thereto. This pressure vessel was placed inan oven regulated so as to have a temperature of 60° C. After 24 hours,the test piece for evaluation was taken out. The test piece was thenair-dried in a draft for further 24 hours.

In the case where the test piece for evaluation did not retain theoriginal shape after the air drying, the chemical resistance thereof wasrated as “poor”. In the case where the test piece for evaluationretained the original shape after the air drying, the chemicalresistance thereof was rated as “good”.

(6) Determination of Phase Angle δ(G*=0.1 MPa) at Absolute Value ofComplex Modulus of Elasticity G*=0.1 MPa

A specimen was placed in a mold for hot pressing which had a thicknessof 1.0 mm. In a hot press having a surface temperature of 180° C.,preheating were conducted for 5 minutes and pressurization anddepressurization were repeated to thereby remove the gas remaining inthe molten resin. Furthermore, the resin was pressed at 4.9 MPa and heldfor 5 minutes. Thereafter, the mold was transferred to a press having asurface temperature of 25° C., and the resin was held for 3 minutes at apressure of 4.9 MPa to thereby cool the resin.

Thus, a pressed specimen plate having a thickness of about 1.0 mm wasproduced. A disk having a diameter of 25 mm was cut out of the pressedspecimen plate, and this disk as a sample was examined for dynamicviscoelasticity using rotational rheometer Type ARES, manufactured byRheometrics Inc., as a device for dynamic viscoelasticity measurement ina nitrogen atmosphere under the following conditions.

Plate: parallel plate having a diameter of 25 mm

Temperature: 160° C.

Strain: 10%

Range of measuring angular frequencies: 1.0×10⁻² to 1.0×10² rad/s

Measuring interval: 5 points/decade

The phase angle δ was plotted against log G*, which is the commonlogarithm of the absolute value G*(Pa) of the complex modulus ofelasticity, and the value of δ (degrees) of any point corresponding tolog G*=5.0 was taken as δ(G*=0.1 MPa). In the case where the measuringpoints included no point which corresponded to log G*=5.0, the twopoints which were located respectively before and after log G*=5.0 wereused to determine a value of δ for log G*=5.0 by linear interpolation.In the case where all the measuring points were log G*<5, the values forthe three points which were the largest three in log G* were used todetermine a value of δ for log G*=5.0 by extrapolation with a quadraticcurve.

(7) Amount of Aluminum (Al)

The amount of aluminum (Al) contained in each polar-group-containingolefin copolymer can be determined by: a method in which the amountthereof is calculated by dividing the amount of the aluminum (Al)contained in the alkylaluminum that was supplied for the polymerizationby the amount of the polar-group-containing olefin copolymer obtained;and a method in which the amount thereof is determined by fluorescentX-ray analysis.

[1] Method for Calculation from Amount of Alkylaluminum Added forPolymerization

Specifically, the aluminum content was calculated using the followingcalculation formula.

Unit of aluminum(Al)content:μg_(Al)/g

(The unit μg_(Al)/g means the amount, in μg, of aluminum (Al) containedin 1 g of the polar-group-containing olefin copolymer.)

μg_(Al) =n×Mw(Al)×10³(μg)

n: Addition amount of alkylaluminum supplied for polymerization (mmol)Mw(Al): Molecular weight of aluminum (Al) element (26.9 g/mol)

[2] Method for Determination by Fluorescent X-Ray Analysis

The amount of the aluminum (Al) contained in each polar-group-containingolefin copolymer was determined using fluorescent X-ray analysis. Adetailed explanation was given hereinabove.

Example 1-1 Synthesis of Drent Type Ligand(2-Isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)

A hexane solution of n-butyllithium (2.5 M; 10 mL; 25.3 mmol) wasgradually added dropwise at 0° C. to a tetrahydrofuran (20 mL) solutionof benzenesulfonic acid anhydride (2 g; 12.6 mmol), and this mixture wasstirred for 1 hour while elevating the temperature thereof to roomtemperature. This liquid reaction mixture was cooled to −78° C., andphosphorus trichloride (1.0 mL; 12.6 mmol) was added thereto. Thismixture was stirred for 2 hours (liquid reaction mixture A).

Magnesium was dispersed in tetrahydrofuran (20 mL), and1-bromo-2-methoxybenzene (2.3 g; 12.6 mmol) was added thereto. Theresultant mixture was stirred at room temperature for 3 hours. Thissolution was added dropwise at −78° C. to the liquid reaction mixture Aprepared above, and the resultant mixture was stirred for 1 hour (liquidreaction mixture B).

A hexane solution of n-butyllithium (2.5 M; 5.0 mL; 12.6 mmol) wasgradually added dropwise at −30° C. to a diethyl ether (20 mL) solutionof 1-bromo-2-isopropylbenzene (2.5 g; 12.6 mmol), and the mixture wasstirred at room temperature for 2 hours. This solution was addeddropwise at −78° C. to the liquid reaction mixture B prepared above, andthe resultant mixture was stirred at room temperature overnight. LC-MSpurity, 60%.

Water (50 mL) was added thereto, and hydrochloric acid was added theretoto render the mixture acidic (pH<3). Thereafter, the mixture wasextracted with methylene chloride (100 mL), and the extract was driedwith sodium sulfate. The solvent was distilled off. The reaction productwas recrystallized with methanol to thereby obtain 1.1 g of the desiredsubstance (I) as a white solid. Yield, 22%.

¹H NMR (CDCl₃, ppm): 8.34 (t, J=6.0 Hz, 1H), 7.7-7.6 (m, 3H), 7.50 (t,J=6.4 Hz, 1H), 7.39 (m, 1H), 7.23 (m 1H), 7.1-6.9 (m, 5H), 3.75 (s, 3H),3.05 (m, 1H), 1.15 (d, J=6.8 Hz, 3H), 1.04 (d, J=6.4 Hz, 3H). ³¹P NMR(CDCl₃, ppm): −10.5.

Formation of Complex

Into a 30-mL flask which had undergone sufficient nitrogen displacementwere introduced 100 μmol of palladium bisdibenzylideneacetone and 100μmol of the phosphorus-sulfonic acid ligand (I). Thereto was addeddehydrated toluene (10 mL). Thereafter, this mixture was treated with anultrasonic vibrator for 10 minutes to thereby prepare a catalyst slurry.

Copolymerization of Ethylene with 1,2-Epoxy-9-decene

The atmosphere within an autoclave having a capacity of 2.4 L andequipped with stirring blades was replaced with purified nitrogen.Thereafter, dry toluene (1.0 L) and 36 mL (0.2 mol) of1,2-epoxy-9-decene were introduced thereinto. While stirring thecontents, the autoclave was heated to 100° C. and nitrogen was suppliedto 0.3 MPa. Thereafter, ethylene was fed to a pressure of 1.3 MPa so asto result in a partial ethylene pressure of 1 MPa. After completion ofthe pressure regulation, 150 μmol of the transition metal complex (I—Pdcomplex) was forced into the autoclave with nitrogen to initiatecopolymerization. During the reaction, the temperature was kept at 100°C. and ethylene was continuously fed so as to maintain the pressure. Themonomers were thus polymerized for 120 minutes. Thereafter, theautoclave was cooled and depressurized to terminate the reaction. Thereaction solution was poured into 1 L of acetone to precipitate apolymer. The resultant polymer was recovered through filtration andwashing and then dried at 60° C. under vacuum until a constant weightwas reached.

The conditions and results of the polymerization are shown in Table 1,and the results of the property examinations are shown in Table 2. InTable 2, “ND” means “not determined” (the same applies thereinafter). InTable 1, the polymerization activity indicates the amount (g) of thecopolymer yielded per mol of the complex used for the polymerization.Incidentally, the polymerization activity was calculated on theassumption that the ligand and the palladium bisdibenzylideneacetone hadreacted in a ratio of 1:1 to form the palladium complex.

Example 1-2 Copolymerization of Ethylene with4-Vinyl-1,2-epoxycyclohexane

The same procedure as in Example 1-1 was conducted, except that 20.9 mL(0.2 mol) of 4-vinyl-1,2-epoxycyclohexane was used as apolar-group-containing comonomer and the amount of the transition metalcomplex was changed to 50 and that the polymerization pressure,polymerization temperature, and polymerization period were 2.3 MPa, 100°C., and 240 minutes, respectively. The conditions and results of thepolymerization are shown in Table 1, and the results of the propertyexaminations are shown in Table 2.

Example 1-3 Copolymerization of Ethylene with 4-Hydroxybutyl AcrylateGlycidyl Ether (4-HBAGE)

The same procedure as in Example 1-1 was conducted, except that 54 mL(0.3 mol) of 4-HBAGE was used as a polar-group-containing comonomer, theamount of the transition metal complex was changed to 50 μmol, and thepolymerization temperature and the polymerization period were changed to90° C. and 70 minutes, respectively. The conditions and results of thepolymerization are shown in Table 1, and the results of the propertyexaminations are shown in Table 2.

Example 1-4 Synthesis of SHOP Type Ligand B-27DM

Ligand B-27DM, which is shown below, was obtained in accordance with themethod described in International Publication WO 2010/050256 (SynthesisExample 4).

Formation of Complex

Into a 50-mL eggplant type flask which had undergone sufficient nitrogendisplacement was introduced 112 mg (200 μmol) of the B-27DM shown below.Next, 56 mg (200 mop of bis-1,5-cyclooctadienenickel(0) (hereinafterreferred to as Ni(COD)2) was introduced into a 50-mL eggplant type flaskand dissolved in 20 mL of dry toluene to prepare a 10-mmol/L toluenesolution of Ni(COD)2. The whole Ni(COD)2 toluene solution (20 mL)obtained here was introduced into the eggplant type flask containing theB-27DM, and the mixture was stirred for 30 minutes on a 40° C. waterbath, thereby obtaining 20 mL of a 10-mmol/L solution of a product ofreaction between the B-27DM and the Ni(COD)2.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 36.6 mg (0.1 mmol) oftri-n-octylaluminum (TNOA), and 2.7 mL (15 mmol) of 4-HBAGE. Whilestirring the contents, the autoclave was heated to 100° C. and nitrogenwas supplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of2.8 MPa so as to result in a partial ethylene pressure of 2.5 MPa. Afterthe temperature and the pressure had become stable, 2.4 mL (24 μmol) ofthe B-27DM/Ni complex solution prepared above was forced into theautoclave with nitrogen to initiate copolymerization. During thereaction, the temperature was kept at 100° C. and ethylene wascontinuously fed so as to maintain the pressure. The monomers werepolymerized for 80 minutes. Thereafter, the autoclave was cooled anddepressurized to terminate the reaction. The reaction solution waspoured into 1 L of acetone to precipitate a polymer. The resultantpolymer was recovered through filtration and washing and then dried at60° C. under vacuum until a constant weight was reached. Thus, thepolar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 28 g. The conditions and results of the polymerization areshown in Table 1, and the results of the property examinations are shownin Table 2. In Table 1, the polymerization activity indicates the amount(g) of the copolymer yielded per mol of the complex used for thepolymerization. Incidentally, the polymerization activity was calculatedon the assumption that the B-27DM and the Ni(COD)2 had reacted in aratio of 1:1 to form the nickel complex. The 4-HBAGE subjected to thecopolymerization was one which had been dehydrated with molecular sieve3A.

Examples 1-5 to 1-12

Polar-group-containing olefin copolymers of Examples 1-5 to 1-12 wereprepared by conducting polymerization in the same manner as in Example1-4, except that the amount of the ligand, concentration of thepolar-group-containing monomer, polymerization temperature, andpolymerization period were changed. The conditions and results of thepolymerization are shown in Table 1, and the results of the propertyexaminations are shown in Table 2.

Examples 1-13 to 1-15

Polymerization was conducted basically in the same manner as in Example1-4, except that the ethylene replenishment after initiation of thepolymerization was omitted. The amount of the ligand, concentration ofthe polar-group-containing monomer, polymerization temperature, andpolymerization period were changed in performing the polymerization.Thus, polar-group-containing olefin copolymers of Examples 1-13 to 1-15were prepared. The conditions and results of the polymerization areshown in Table 1, and the results of the property examinations are shownin Table 2. In this polymerization method, the partial ethylene pressureat the time of termination of the polymerization is lower than that atthe time of the polymerization initiation because ethylene replenishmentis omitted. The expression “2.5→1.5” in the column “Partial ethylenepressure” in Table 1 indicates that the partial ethylene pressure atpolymerization initiation was 2.5 MPa and the partial ethylene pressureat polymerization termination was 1.5 MPa (the same applieshereinafter).

Example 1-16 Synthesis of SHOP Type Ligand2-(2,6-Diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114)

Ligand B-114, which is shown below, was obtained in accordance with themethod described in JP-A-2013-043871 (Synthesis Example 4).

Formation of Complex

Into a 50-mL eggplant type flask which had undergone sufficient nitrogendisplacement was introduced 145 mg (200 μmol) of the2-(2,6-diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114) shown above. Next, 56 mg (200 μmol) ofbis-1,5-cyclooctadienenickel(0) (hereinafter referred to as Ni(COD)2)was introduced into a 50-mL eggplant type flask and dissolved in 20 mLof dry toluene to prepare a 10-mmol/L toluene solution of Ni(COD)2. Thewhole Ni(COD)2 toluene solution (20 mL) obtained here was introducedinto the eggplant type flask containing the B-114, and the mixture wasstirred for 30 minutes on a 40° C. water bath, thereby obtaining 20 mLof a 10-mmol/L solution of a product of reaction between the B-114 andthe Ni(COD)2.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 36.6 mg (0.10 mmol) oftri-n-octylaluminum (TNOA), and 1.8 mL (10 mmol) of 4-HBAGE. Whilestirring the contents, the autoclave was heated to 90° C. and nitrogenwas supplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of2.8 MPa so as to result in a partial ethylene pressure of 2.5 MPa. Afterthe temperature and the pressure had become stable, 2.0 mL (20 μmol) ofthe B-114/Ni complex solution prepared above was forced into theautoclave with nitrogen to initiate copolymerization. During thereaction, the temperature was kept at 90° C. The monomers werepolymerized for 46 minutes. Thereafter, the autoclave was cooled anddepressurized to terminate the reaction. The reaction solution waspoured into 1 L of acetone to precipitate a polymer. The resultantpolymer was recovered through filtration and washing and then dried at60° C. under vacuum until a constant weight was reached. Thus, thepolar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 32 g.

The conditions and results of the polymerization are shown in Table 1,and the results of the property examinations are shown in Table 2. InTable 1, the polymerization activity indicates the amount (g) of thecopolymer yielded per mol of the complex used for the polymerization. Inthis polymerization method, the partial ethylene pressure at the time oftermination of the polymerization is lower than that at the time of thepolymerization initiation because ethylene replenishment is omitted.

Incidentally, the polymerization activity was calculated on theassumption that the B-114 and the Ni(COD)2 had reacted in a ratio of 1:1to form the nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Comparative Example 1-1 Homopolymerization of Ethylene

The same procedure as in Example 1-4 was conducted, except that neitherthe polar-group-containing comonomer nor tri-n-octylaluminum (TNOA) wasused and the amount of the transition metal complex was changed to 0.2μmol, and that the polymerization pressure, polymerization temperature,and polymerization period were 3.0 MPa, 100° C., and 30 minutes,respectively. The conditions and results of the polymerization are shownin Table 1, and the results of the property examinations are shown inTable 2.

Comparative Example 1-2

This Comparative Example is a polar-group-containing olefin copolymer(trade name: Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.)which is a copolymer of ethylene with glycidyl methacrylate and wasproduced by a high-pressure process. The results of the propertyexaminations are shown in Table 2.

Comparative Example 1-3

This Comparative Example is a polar-group-containing olefin copolymer(trade name: Bondfast 2C, manufactured by Sumitomo Chemical Co., Ltd.)which is a copolymer of ethylene with glycidyl methacrylate and wasproduced by a high-pressure process. The results of the propertyexaminations are shown in Table 2.

TABLE 1 Polymerization conditions Amount Amount of polar- Parital Tem-of group-containing ethylene pera- Amount Catalytic Kind of ligand TNOAKind of polar-group- monomer pressure ture Period yielded efficiency Runligand μmol mmol containing monomer mmol mL MPa ° C. min g g/mol ExampleI 150 — 1,2-epoxy-9-decene 200 25 1.0 100 120 72 4.8E+05 1-1 Example I50 — 1,2-epoxy-4-vinyl- 200 21 2.0 100 240 85 1.7E+06 1-2 cyclohexaneExample I 50 — 4-hydroxybutyl acrylate 300 54 1.0 90 70 58 1.2E+06 1-3glycidylether Example B27DM 24 0.1 4-hydroxybutyl acrylate 15 2.7 2.5100 80 28 1.2E+06 1-4 glycidylether Example B27DM 30 0.15 4-hydroxybutylacrylate 15 2.7 2.5 105 60 38 1.3E+06 1-5 glycidylether Example B27DM 300.1 4-hydroxybutyl acrylate 15 2.7 2.5 110 61 45 1.5E+06 1-6glycidylether Example B27DM 20 0.1 4-hydroxybutyl acrylate 15 2.7 2.5 9050 41 2.0E+06 1-7 glycidylether Example B27DM 100 0.2 4-hydroxybutylacrylate 50 9.1 2.5 90 120 10 9.8E+04 1-8 glycidylether Example B27DM380 0.4 4-hydroxybutyl acrylate 50 9.1 2.0 90 120 60 1.6E+05 1-9glycidylether Example B27DM 100 0.2 4-hydroxybutyl acrylate 50 9.1 2.090 80 34 3.4E+05 1-10 glycidylether Example B27DM 100 0.2 4-hydroxybutylacrylate 50 9.1 2.0 90 251 35 3.5E+05 1-11 glycidylether Example B27DM100 0.2 4-hydroxybutyl acrylate 50 9.1 2.0 90 304 49 4.9E+05 1-12glycidylether Example B27DM 30 0.2 4-hydroxybutyl acrylate 5 0.912.5→1.5 105 50 33 1.1E+06 1-13 glycidylether Example B27DM 3 0.14-hydroxybutyl acrylate 0.5 0.091 2.5→1.5 105 33 37 1.2E+07 1-14glycidylether Example B27DM 300 0.1 4-hydroxybutyl acrylate 0.05 9.12.5→1.3 110 210 43.7 1.5E+05 1-15 glycidylether Example B114 20 0.14-hydroxybutyl acrylate 0.01 1.82 2.5→1.5 90 46 32.3 1.6E+06 1-16glycidylether Compara- B27DM 0.2 — — — — 3.0 100 30 5 2.6E+07 tiveExample 1-1

TABLE 2 Amount of residual aluminum Calculated from Determined Amount ofamount of by Weight-average Molecular-weight polar-group alkylaluminumfluorescent molecular distribution δ Adhesion strength strucural addedfor X-ray Kind of polar-group- weight parameter Melting point (G* = 0.1MPa) Polyamide EVOH Polyester Fluororesin unit Chemical polymerizationanalysis containing monomer Mw*10⁻⁴ Mw/Mn ° C. ° gf/10 mm mol %resistance μg_(Al)/g_(PE) μg_(Al)/g_(PE) Example 1-1 1,2-epoxy-9-decene4.9 2.82 122.8 ND peeling ND ND ND 0.71 good 0.0 ND impossible Example1-2 1, 2-epoxy-4-vinyl- 10.0 2.04 130.9 63.3 650 ND ND ND 0.08 good 0.0ND cyclohexane Example 1-3 4-hydroxybutyl acrylate 8.0 2.68 122.2 NDpeeling ND ND ND 0.78 good 0.0 ND glycidylether impossible Example 1-44-hydroxybutyl acrylate 7.5 2.17 121.1 ND peeling ND ND ND 0.95 good97.8 ND glycidylether impossible Example 1-5 4-hydroxybutyl acrylate 7.02.09 122.3 ND peeling ND ND ND 0.82 good 106.8 ND glycidyletherimpossible Example 1-6 4-hydroxybutyl acrylate 6.0 2.35 122.8 48.1peeling ND ND ND 0.78 good 60.2 ND glycidylether impossible Example 1-74-hydroxybutyl acrylate 13.1 2.35 122.4 ND peeling ND ND ND 1.04 good66.0 ND glycidylether impossible Example 1-8 4-hydroxybutyl acrylate 7.62.40 105.1 47.4 3500 ND ND ND 3.66 good 550.6 ND glycidylether Example1-9 4-hydroxybutyl acrylate 11.2 2.46 119.2 48.7 950 ND ND ND 2.22 good180.2 171.0 glycidylether Example 1-10 4-hydroxybutyl acrylate 9.1 2.46110.0 48.2 4030 ND ND ND 3.20 good 158.2 ND glycidylether Example 1-114-hydroxybutyl acrylate 7.3 2.49 104.6 49.6 4800 780 1080 2530 3.80 good152.9 ND glycidylether Example 1-12 4-hydroxybutyl acrylate 9.2 2.24112.4 49.2 2850 400 550 1700 2.46 good 110.5 ND glycidylether Example1-13 4-hydroxybutyl acrylate 6.6 2.01 125.4 62.5 peeling ND ND ND 0.33good 164.5 ND glycidylether impossible Example 1-14 4-hydroxybutylacrylate 6.8 1.97 130.8 ND 850 ND ND ND 0.03 good 72.1 ND glycidyletherExample 1-15 4-hydroxybutyl acrylate 3.02 2.18 114.3 ND 22 ND ND ND 3.04good 61.7 ND glycidylether Example 1-16 4-hydroxybutyl acrylate 2.8 2.35127.8 ND 65 ND ND ND 0.24 good 83.5 ND glycidylether Comparative — 10.12.04 131.3 ND 0 ND ND ND 0.00 good 0.0 ND Example 1-1 Comparativeglycidyl methacrylate 10.6 5.17 99.2 37.3 4000 ND ND ND 2.99 poor 0.0 NDExample 1-2 Comparative glycidyl methacrylate 12.0 5.92 105.6 36.2 3800ND ND ND 1.43 poor 0.0 ND Example 1-3

Discussion on the Results of the Examples and Comparative Examples

Example 1-1 to Example 1-16 each have an amount of polar-groupstructural units of 0.001 mol % or larger and have practicallysufficient adhesiveness of the polyamide.

Furthermore, Example 1-1 to Example 1-14 each have a weight-averagemolecular weight (Mw) of 33,000 or higher and show excellentadhesiveness to the polyamide. In contrast, Comparative Example 1contains no polar group and does not adhere to the polyamide at all. Itwas thus demonstrated that a polar-group-containing olefin copolymer hassufficient adhesiveness to highly polar bases so long as the amount ofpolar-group structural units contained in the copolymer is 0.001 mol %or large.

Examples 1-1 to 1-3, Examples 1-4 to 1-15, and Example 1-16 arepolar-group-containing olefin copolymers produced by differentproduction processes. These polar-group-containing olefin copolymers,although produced by different production processes, each showsufficient adhesiveness. This fact showed that for producing apolar-group-containing olefin copolymer having sufficiently highadhesiveness to highly polar materials, any process in which monomersare polymerized in the presence of a specific transition metal catalystcan be used without particular limitations and that processes forproducing the polar-group-containing olefin copolymer according to theinvention are not limited.

Example 1-11 and Example 1-12 have practically sufficient adhesivenessnot only to the polyamide resin but also to the EVOH, polyester, andfluororesin. This fact has made it clear that materials to which thepolar-group-containing olefin copolymer of the invention hasadhesiveness are not limited to a specific highly polar material, andthe copolymer has sufficient adhesiveness to highly polar materials ofvarious kinds.

Example 1-1 to Example 1-16 have high adhesiveness and, despite this,show sufficient chemical resistance. In contrast, Comparative Example1-2 and Comparative Example 1-3 have insufficient chemical resistancealthough satisfactory in terms of adhesiveness. The cause of this ispresumed to be a difference in molecular structure. Example 1-1 toExample 1-16 have a linear molecular structure since the copolymers wereproduced in the presence of a transition metal catalyst. In contrast,Comparative Example 1-2 and Comparative Example 1-3 are known to havebeen produced by a high-pressure process, and these copolymers arethought to have a molecular structure which has too large an amount ofshort-chain branches and long-chain branches. It is thought that thisdifference in structure brought about a difference in the swellabilityof the amorphous portions by chemicals, resulting in the difference inchemical resistance. These results have demonstrated that thepolar-group-containing olefin copolymer according to the invention is apolar-group-containing olefin copolymer which not only has highadhesiveness to highly polar materials but also is prominent in chemicalresistance.

The predominance and rationality of the configurations of the invention(characterizing features of the invention) and the superiority thereofto prior-art techniques have been rendered clear by the satisfactoryresults of the Examples given above and by comparisons between theExamples and the Comparative Examples.

Experiment Example 2 Evaluation of Polar-Group-Containing MultinaryOlefin Copolymers (B) (1) Amount of Polar-Group-Containing StructuralUnits

The amount of polar-group-containing structural units was determinedusing a ¹H-NMR spectrum. Specifically, the amount thereof was determinedby the method described in Experiment Example 1 and hereinabove.

(2) Weight-Average Molecular Weight (Mw) and Molecular-WeightDistribution Parameter (Mw/Mn)

Weight-average molecular weight (Mw) was determined by gel permeationchromatography (GPC). Molecular-weight distribution parameter (Mw/Mn)was determined by further determining the number-average molecularweight (Mn) by gel permeation chromatography (GPC) and calculating theratio between Mw and Mn, i.e., Mw/Mn. Specifically, the molecular weightand the parameter were determined by the method described in ExperimentExample 1 and hereinabove.

(3) Melting Point

Melting point is expressed by the peak temperature in an endothermiccurve determined with a differential scanning calorimeter (DSC). Themeasurement was made through the same steps as in Experiment Example 1.

(4) Adhesion Strength

Adhesion strength was measured by preparing both a pressed plate of atest sample and various base films, stacking and hot-pressing thepressed plate and each of the base films to thereby produce a layeredproduct, and subjecting the layered product to a peel test. Themeasurement was made through the same steps as in Experiment Example 1.

(5) Tensile Impact Strength [1] Method for Producing Test Sample forTensile Impact Strength

Pellets of each of the resin compositions of the Examples andComparative Examples were placed in a mold for hot pressing which had athickness of 1 mm. In a hot press having a surface temperature of 230°C., preheating was conducted for 5 minutes and pressurization anddepressurization were repeated to thereby melt the resin and remove thegas remaining in the molten resin. Furthermore, the resin was pressed at4.9 MPa and held for 5 minutes. Thereafter, the resin in the state ofbeing pressed at 4.9 MPa was gradually cooled at a rate of 10° C./min.At the time when the temperature had declined to around roomtemperature, the molded plate was taken out of the mold. The moldedplate obtained was conditioned for 48 hours or longer in an atmospherehaving a temperature of 23±2° C. and a humidity of 50±5° C. Test pieceshaving the shape of ASTM D1822 Type-S were punched out of theconditioned pressed plate to obtain a test sample for tensile impactstrength.

[2] Conditions for Tensile Impact Strength Test

The test pieces were used to measure the tensile impact strength thereofby reference to JIS K 7160-1996, Method B. Incidentally, the shape ofthe test pieces is the only point in which the conditions were differentfrom those in JIS K 7160-1996. With respect to the other conditions,etc., the test was performed by a method according to JIS K 7160-1996.

(6) Determination of δ(G*=0.1 MPa) by Dynamic ViscoelasticityMeasurement

δ(G*=0.1 MPa) was determined by a dynamic viscoelasticity measurementthrough the same steps as in Experiment Example 1.

(7) Amount of Aluminum (Al)

The amount of the aluminum (Al) contained in each polar-group-containingmultinary olefin copolymer was determined through the same steps as inExperiment Example 1.

Example 2-1 Synthesis of SHOP Type Ligand (B-27DM)

A SHOP type ligand (B-27DM) was synthesized in the same manner as inExample 1-4.

Formation of Complex

A product of reaction between the B-27DM and Ni(COD)2 was obtained inthe same manner as in Example 1-4.

(Copolymerization for Producing Ethylene/4-Hydroxybutyl AcrylateGlycidyl Ether (4-HBAGE)/n-Butyl Acrylate Terpolymer)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 36.6 mg (0.1 mmol) oftri-n-octylaluminum (TNOA), 3.6 mL (20 mmol) of 4-HBAGE, and 7.1 mL (50mmol) of n-butyl acrylate. While stirring the contents, the autoclavewas heated to 80° C. and nitrogen was supplied to 0.4 MPa. Thereafter,ethylene was fed to a pressure of 2.8 MPa so as to result in a partialethylene pressure of 2.4 MPa. After the temperature and the pressure hadbecome stable, 10 mL (100 μmol) of the B-27DM-Ni complex solutionprepared above was forced into the autoclave with nitrogen to initiatecopolymerization. During the reaction, the temperature was kept at 80°C. and ethylene was continuously fed so as to maintain the pressure. Themonomers were polymerized for 180 minutes. Thereafter, the autoclave wascooled and depressurized to terminate the reaction. The reactionsolution was poured into 1 L of acetone to precipitate a polymer. Theresultant polymer was recovered through filtration and washing and thendried at 60° C. under vacuum until a constant weight was reached. Thus,the polar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 19.4 g. The conditions and results of the polymerization areshown in Table 3, and the results of the property examinations are shownin Table 4. The polymerization activity was calculated on the assumptionthat the B-27DM and the Ni(COD)2 had reacted in a ratio of 1:1 to formthe nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Example 2-2, Comparative Example 2-1, and Comparative Example 2-2

Polar-group-containing olefin copolymers of Example 2-2, ComparativeExample 2-1, and Comparative Example 2-2 were prepared by conductingpolymerization in the same manner as in Example 2-1, except that theamount of the ligand, kinds of the comonomers, monomer concentrations,polymerization temperature, and polymerization period were changed. Theconditions and results of the polymerization are shown in Table 3, andthe results of the property examinations are shown in Table 4.

Example 2-3 Synthesis of SHOP Type Ligand (B-111)

Ligand B-111, which is shown below, was obtained in accordance withJP-A-2013-043871 (Synthesis Example 1).

Formation of Complex

Into a 50-mL eggplant type flask which had undergone sufficient nitrogendisplacement was introduced 137 mg (200 μmol) of the B-111 shown below.Next, 56 mg (200 μmol) of bis-1,5-cyclooctadienenickel(0) (hereinafterreferred to as Ni(COD)2) was introduced into a 50-mL eggplant type flaskand dissolved in 20 mL of dry toluene to prepare a 10-mmol/L toluenesolution of Ni(COD)2. The whole Ni(COD)2 toluene solution (20 mL)obtained here was introduced into the eggplant type flask containing theB-27DM, and the mixture was stirred for 30 minutes on a 40° C. waterbath, thereby obtaining 20 mL of a 10-mmol/L solution of a product ofreaction between the B-111 and the Ni(COD)2.

(Copolymerization for Producing Ethylene/4-Hydroxybutyl AcrylateGlycidyl Ether (4-HBAGE)/n-Butyl Acrylate Terpolymer)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 54.9 mg (0.15 mmol) oftri-n-octylaluminum (TNOA), 3.96 mL (22 mmol) of 4-HBAGE, and 19.9 mL(140 mmol) of n-butyl acrylate. While stirring the contents, theautoclave was heated to 70° C. and nitrogen was supplied to 0.4 MPa.Thereafter, ethylene was fed to a pressure of 2.8 MPa so as to result ina partial ethylene pressure of 2.4 MPa. After the temperature and thepressure had become stable, 18 mL (180 μmol) of the B-111-Ni complexsolution prepared above was forced into the autoclave with nitrogen toinitiate copolymerization. During the reaction, the temperature was keptat 70° C. and ethylene was continuously fed so as to maintain thepressure. The monomers were polymerized for 120 minutes. Thereafter, theautoclave was cooled and depressurized to terminate the reaction. Thereaction solution was poured into 1 L of acetone to precipitate apolymer. The resultant polymer was recovered through filtration andwashing and then dried at 60° C. under vacuum until a constant weightwas reached. Thus, the polar-group-containing monomer which had remainedin the polar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 21.0 g. The conditions and results of the polymerization areshown in Table 3, and the results of the property examinations are shownin Table 4. The polymerization activity was calculated on the assumptionthat the B-111 and the Ni(COD)2 had reacted in a ratio of 1:1 to formthe nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Example 2-4

A polar-group-containing olefin copolymer of Example 2-4 was prepared byconducting polymerization in the same manner as in Example 2-3, exceptthat the amount of the ligand, kinds of the comonomers, monomerconcentrations, polymerization temperature, and polymerization periodwere changed. The conditions and results of the polymerization are shownin Table 3, and the results of the property examinations are shown inTable 4.

Comparative Example 2-3

This Comparative Example is an olefin copolymer (trade name: KernelKF370, manufactured by Japan Polyethylene Corp.) which is a copolymer ofethylene, propylene, and hexene and was produced with ametallocene-based catalyst. The results of the property examinations areshown in Table 4.

Comparative Example 2-4

This Comparative Example is a polar-group-containing olefin copolymer(trade name: Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.)which is a copolymer of ethylene with glycidyl methacrylate and wasproduced by a high-pressure process. The results of the propertyexaminations are shown in Table 4.

Comparative Example 2-5

This Comparative Example is a polar-group-containing olefin copolymer(trade name: Bondfast 2C, manufactured by Sumitomo Chemical Co., Ltd.)which is a copolymer of ethylene with glycidyl methacrylate and wasproduced by a high-pressure process. The results of the propertyexaminations are shown in Table 4.

TABLE 3 Polymerization conditions Amount Tem- of pera- Amount Kind ofligand TNOA Comonomer Z1 Comonomer Z2 pressure ture Period yieldedActivity Run ligand μmol mmol mol/L mol/L MPa ° C. min g g/mol MPahExample B27DM 100 0.1 4-hydroxybutyl 0.020 n-buthyl 0.050 2.4 80 18019.4 2.7E+04 2-1 acrylate acrylate glycidylether Example B27DM 100 0.14-hydroxybutyl 0.020 n-buthyl 0.050 2.4 80 90 11.5 3.2E+04 2-2 acrylateacrylate glycidylether Example B111 180 0.15 4-hydroxybutyl 0.022n-buthyl 0.140 2.4 70 120 21.0 2.4E+04 2-3 acrylate acrylateglycidylether Example B111 30 0.2 4-hydroxybutyl 0.006 n-buthyl 0.0042.5 80 134 23.5 1.4E+05 2-4 acrylate acrylate glycidylether Compara-B27DM 360 0.4 4-hydroxybutyl 0.050 — — 2.0 95 110 58.2 4.4E+04 tiveacrylate Example glycidylether 2-1 Compara- B27DM 200 0.2 4-hydroxybutyl0.050 — — 2.0 90 152 39.8 3.9E+04 tive acrylate Example glycidylether2-2

TABLE 4 Amount of residual aluminum Amount of Calculated from DeterminedMolecular polar-group amount of by Weight-average weight structuralalkylaluminum fluorescent molecular distribution units δ added for X-rayTensile impact Adhesion strength weight parameter [Z1] Melting point128-6.0 [Z1] (G* = 0.1 MPa) polymerization analysis strength FluororesinPolyamide Comonomer Z1 Comonomer Z2 Mw*10⁻⁴ Mw/Mn mol % ° C. ° C. °μg_(Al)/g μg_(Al)/g kJ/m² gf/10 mm gf/10 mm Example 2-1 4-hydroxybutylbutyl 5.6 2.33 1.80 101.3 117.2 ND 139 ND 950 2292 ND acrylate acrylateglycidylether Example 2-2 4-hydroxybutyl butyl 5.5 2.63 1.83 98.6 117.0ND 235 ND 1010 2700 ND acrylate acrylate glycidylether Example 2-34-hydroxybutyl butyl 5.3 1.96 1.46 94.8 119.2 ND 193 184 1106 2575 NDacrylate acrylate glycidylether Example 2-4 4-hydroxybutyl butyl 14.52.10 0.21 125.7 126.7 56.7 230 ND 1551 ND 2010 acrylate acrylateglycidylether Comparative 4-hydroxybutyl — 11.2 2.46 2.22 119.2 114.748.7 185 171 1210 265 1125 Example 2-1 acrylate glycidyletherComparative 4-hydroxybutyl — 8.3 2.45 3.23 112.4 108.6 50.0 136 ND 1068350 950 Example 2-2 acrylate glycidylether Comparative — pro- 8.4 2.100.00 97.0 — 63.2 0 ND 2228 0 0 Example 2-3 pylene, 1-hexane Comparativeglycidyl — 10.6 5.17 2.99 99.2 — 37.3 0 ND 465 2000 3850 Examplemethacrylate 2-4 Comparative glycidyl — 12.0 5.92 1.46 105.6 — 36.2 0 ND240 420 550 Example methacrylate 2-5

Discussion on the Results of the Examples and Comparative Examples

It has become clear that Example 2-1 to Example 2-4, which arepolar-group-containing multinary olefin copolymers, show sufficientadhesiveness, whereas Comparative Example 2-3, which is an olefincopolymer having no polar group, shows no adhesiveness at all. Thisindicates that to contain polar groups is essential for exhibitingadhesiveness.

It has become clear that the polar-group-containing multinary olefincopolymers of Example 2-1 to Example 2-4 have markedly improvedadhesiveness as compared with the polar-group-containing binary olefincopolymers of Comparative Example 2-1 and Example 2-2, which have thesame polar groups. This indicates that by rendering a copolymer flexiblewith any third comonomer, the adhesiveness can be improved regardless ofthe polar groups and the kind of the third comonomer.

Example 2-1 to Example 2-4 have high adhesiveness and, despite this,show sufficient impact resistance. In contrast, Comparative Example 2-4and Comparative Example 2-5 have insufficient impact resistance althoughsatisfactory in terms of adhesiveness. The cause of this is presumed tobe a difference in molecular structure. Example 2-1 to Example 2-4 havea linear molecular structure since the copolymers were produced in thepresence of a transition metal catalyst. In contrast, ComparativeExample 2-4 and Comparative Example 2-5 are known to have been producedby a high-pressure process, and these copolymers are thought to have amolecular structure which has too large an amount of short-chainbranches and long-chain branches. It is thought that as a result of suchstructure, the copolymers of the Comparative Examples have reducedimpact resistance.

Those results have demonstrated the usefulness of the copolymer of theinvention which is the polar-group-containing multinary olefin copolymerand which can have improved adhesiveness and improved impact resistancewhile attaining a satisfactory balance therebetween.

Experiment Example 3 Evaluation of Olefin-Based Resin Compositions (D)(1) Amount of Polar-Group-Containing Structural Units inPolar-Group-Containing Olefin Copolymer (A′)

The amount of polar-group-containing structural units was determinedusing a ¹H-NMR spectrum. Specifically, the amount thereof was determinedby the method described in Experiment Example 1 and hereinabove.

(2) Weight-Average Molecular Weight (Mw) and Molecular-WeightDistribution Parameter (Mw/Mn)

Weight-average molecular weight (Mw) was determined by gel permeationchromatography (GPC). Molecular-weight distribution parameter (Mw/Mn)was determined by further determining the number-average molecularweight (Mn) by gel permeation chromatography (GPC) and calculating theratio between Mw and Mn, i.e., Mw/Mn. Specifically, the molecular weightand the parameter were determined by the method described in ExperimentExample 1 and hereinabove.

(3) Melting Point

Melting point is expressed by the peak temperature in an endothermiccurve determined with a differential scanning calorimeter (DSC). Themeasurement was made through the same steps as in Experiment Example 1.

(4) Adhesion Strength

Adhesion strength was measured by preparing both a pressed plate of atest sample and various base films, stacking and hot-pressing thepressed plate and each of the base films to thereby produce a layeredproduct, and subjecting the layered product to a peel test. Themeasurement was made through the same steps as in Experiment Example 1.

(5) Determination of δ(G*=0.1 MPa) by Dynamic ViscoelasticityMeasurement

δ(G*=0.1 MPa) was determined by a dynamic viscoelasticity measurementthrough the same steps as in Experiment Example 1.

(6) Amount of Aluminum (Al)

The amount of the aluminum (Al) contained in each polar-group-containingolefin copolymer (A′) was determined through the same steps as inExperiment Example 1.

(7) Melt Flow Rate (MFR)

MFR was measured in accordance with JIS K7120 (1999) under theconditions of a temperature of 190° C. and a load of 2.16 kg. A detailedexplanation was given hereinabove.

(8) Density

Density was determined in accordance with JIS K7112, Method A (1999). Adetailed explanation was given hereinabove.

Production Example 3-1 Production of Polar-Group-Containing OlefinCopolymer (A′-3-1) Synthesis of SHOP Type Ligand (B-27DM)

A SHOP type ligand (B-27DM) was synthesized in the same manner as inExample 1-4.

Formation of Complex

A product of reaction between the B-27DM and Ni(COD)2 was obtained inthe same manner as in Example 1-4.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 54.9 mg (0.15 mmol) oftri-n-octylaluminum (TNOA), and 2.7 mL (15 mmol) of 4-HBAGE. Whilestirring the contents, the autoclave was heated to 105° C. and nitrogenwas supplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of2.8 MPa so as to result in a partial ethylene pressure of 2.5 MPa. Afterthe temperature and the pressure had become stable, 3.0 mL (30 μmol) ofthe B-27DM-Ni complex solution prepared above was forced into theautoclave with nitrogen to initiate copolymerization. During thereaction, the temperature was kept at 105° C. and ethylene wascontinuously fed so as to maintain the pressure. The monomers werepolymerized for 60 minutes. Thereafter, the autoclave was cooled anddepressurized to terminate the reaction. The reaction solution waspoured into 1 L of acetone to precipitate a polymer. The resultantpolymer was recovered through filtration and washing and then dried at60° C. under vacuum until a constant weight was reached. Thus, thepolar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 38 g. The conditions and results of the polymerization areshown in Table 5, and the results of the property examinations are shownin Table 6. In Table 5, the polymerization activity indicates the amount(g) of the copolymer yielded per mol of the complex used for thepolymerization. Incidentally, the polymerization activity was calculatedon the assumption that the B-27DM and the Ni(COD)2 had reacted in aratio of 1:1 to form the nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Production Examples 3-2 to 3-4 Production of Polar-Group-ContainingOlefin Copolymers (A′-3-2, A′-3-3, and A′-3-4)

Polar-group-containing olefin copolymers of Production Example 3-2 toProduction Example 3-4 were prepared by conducting polymerization in thesame manner as in Production Example 3-1, except that the amount of theligand, concentration of the polar-group-containing monomer,polymerization temperature, and polymerization period were changed. Theconditions and results of the polymerization are shown in Table 5, andthe results of the property examinations are shown in Table 6.

Production Example 3-5 Production of Polar-Group-Containing OlefinCopolymer (A′-3-5)

Polymerization was conducted basically in the same manner as inProduction Example 3-1, except that the ethylene replenishment afterinitiation of the polymerization was omitted. The amount of the ligand,concentration of the polar-group-containing monomer, polymerizationtemperature, and polymerization period were changed in performing thepolymerization. Thus, a polar-group-containing olefin copolymer ofProduction Example 3-5 was prepared. The conditions and results of thepolymerization are shown in Table 5, and the results of the propertyexaminations are shown in Table 6. In this polymerization method, thepartial ethylene pressure at the time of termination of thepolymerization is lower than that at the time of the polymerizationinitiation because ethylene replenishment is omitted.

Production Example 3-6 Production of Polar-Group-Containing OlefinCopolymer (A′-3-6) Synthesis of SHOP Type Ligand2-(2,6-Diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114)

2-(2,6-Diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114) was obtained in the same manner as in Example 1-16.

Formation of Complex

A solution of a complex of the2-(2,6-diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114) with bis-1,5-cyclooctadienenickel(0) (Ni(COD)2) was obtained inthe same manner as in Example 1-16.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

A copolymer of ethylene with 4-hydroxybutyl acrylate glycidyl ether(4-HBAGE) was obtained in the same manner as in Example 1-16.

The conditions and results of the polymerization are shown in Table 5,and the results of the property examinations are shown in Table 6.

Production Example 3-7 Production of Polar-Group-Containing OlefinCopolymer (A′-3-7) Synthesis of Drent Type Ligand(2-Isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)

Drent type ligand(2-isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)was obtained in the same manner as in Example 1-1.

Formation of Complex

Into a 30-mL flask which had undergone sufficient nitrogen displacementwere introduced 100 μmol of palladium bisdibenzylideneacetone and 100μmol of the phosphorus-sulfonic acid ligand (I). Dehydrated toluene (10mL) was added thereto. Thereafter, this mixture was treated with anultrasonic vibrator for 10 minutes to thereby prepare a catalyst slurry.

Copolymerization of Ethylene with 1,2-Epoxy-9-decene

A copolymer of ethylene with 1,2-epoxy-9-decene was obtained in the samemanner as in Example 1-1.

The conditions and results of the polymerization are shown in Table 5,and the results of the property examinations are shown in Table 6.

Production Example 3-8 Production of Polar-Group-Containing OlefinCopolymer (A′-3-8) Copolymerization of Ethylene with 4-HydroxybutylAcrylate Glycidyl Ether (4-HBAGE)

The same procedure as in Production Example 3-7 was conducted, exceptthat 54 mL (0.3 mol) of 4-HBAGE was used as a polar-group-containingmonomer and the amount of the transition metal complex was changed to 50μmol and that the polymerization temperature and the polymerizationperiod were changed to 90° C. and 70 minutes, respectively. Theconditions and results of the polymerization are shown in Table 5, andthe results of the property examinations are shown in Table 6.

Polar-Group-Containing Olefin Copolymer (A′-3-9)

This copolymer is a polar-group-containing olefin copolymer (trade name:Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.) which is acopolymer of ethylene with glycidyl methacrylate and was produced by ahigh-pressure process. The properties of this polar-group-containingolefin copolymer are shown in Table 6.

TABLE 5 Polymerization conditions Amount Amount of polar- Parital Tem-of group-containing ethylene pera- Amount Catalytic Kind of ligand TNOAKind of polar-group- monomer pressure ture Period yielded efficiency Runligand μmol mmol containing monomer mmol mL MPa ° C. min g g/molProduction B27DM 30 0.15 4-hydroxybutyl acrylate 15 2.7 2.5 105 60 381.3E+06 Example glycidylether 3-1 Production B27DM 380 0.44-hydroxybutyl acrylate 50 9.1 2.0 90 120 60 1.6E+05 Exampleglycidylether 3-2 Production B27DM 200 0.2 4-hydroxybutyl acrylate 152.7 2.0 90 152 40 2.0E+05 Example glycidylether 3-3 Production B27DM 1200.2 4-hydroxybutyl acrylate 50 9.1 2.0 90 120 38 3.2E+05 Exampleglycidylether 3-4 Production B27DM 3 0.1 4-hydroxybutyl acrylate 5 0.912.5→1.5 105 33 37 1.2E+07 Example glycidylether 3-5 Production B114 200.10 4-hydroxybutyl acrylate 10 1.8 2.5→1.5 90 46 32 1.6E+06 Exampleglycidylether 3-6 Production I 150 — 1,2-epoxy-9-decene 200 25 1.0 100120 72 4.8E+05 Example 3-7 Production I 50 — 4-hydroxybutyl acrylate 30054 1.0 90 70 58 1.2E+06 Example glycidylether 3-8

TABLE 6 Amount of residual aluminum Molecular- Amount CalculatedDetermined Weight- weight of polar- from amount of by fluo- averagedistri- group alkylaluminum rescent molecular bution Melting δ struc-added for X-ray Kind of polar-group- weight parameter point (G* = 0.1MPa) ural unit polymerization analysis Run Name containing monomerMw*10⁻⁴ Mw/Mn ° C. ° mol % μg_(Al)/g_(PE) μg_(Al)/g_(PE) ProductionA′-3-1 4-hydroxybutyl acrylate 7.0 2.20 122.3 ND 0.82 106.8 ND Exampleglycidylether 3-1 Production A′-3-2 4-hydroxybutyl acrylate 11.2 2.28119.2 48.7 2.22 180.2 171 Example glycidylether 3-2 Production A′-3-34-hydroxybutyl acrylate 8.2 2.46 112.4 50.0 3.23 135.6 ND Exampleglycidylether 3-3 Production A′-3-4 4-hydroxybutyl acrylate 8.8 2.45114.9 ND 2.68 142.0 ND Example glycidylether 3-4 Production A′-3-54-hydroxybutyl acrylate 6.83 2.41 130.8 ND 0.03 72.1 ND Exampleglycidylether 3-5 Production A′-3-6 4-hydroxybutyl acrylate 2.81 2.35127.8 ND 0.24 83.5 ND Example glycidylether 3-6 Production A′-3-71,2-epoxy-9-decene 8 2.68 122.2 ND 0.78 0.0 ND Example 3-7 ProductionA′-3-8 4-hydroxybutyl acrylate 4.9 2.80 122.8 ND 0.71 0.0 ND Exampleglycidylether 3-8 — A′-3-9 glycidyl methacrylate 10.6 5.17 99.2 37.32.99 0.0 ND

Example 3-1

The polar-group-containing olefin copolymer (A′-3-1) was dry-blended inan amount of 0.05 g with 9.95 g of linear low-density polyethylene(trade name: F30FG (referred to as “LLDPE” in the table), manufacturedby Japan Polyethylene Corp.). This mixture was introduced into a compacttwin-screw kneader (Type: MC15, manufactured by DSM Xplore) andmelt-kneaded for 5 minutes. For this kneading, the barrel temperatureand the screw rotation speed were set at 180° C. and 100 rpm,respectively. After the 5 minutes, a rod-shaped resin composition wasextruded through the resin discharge port. This resin composition wasplaced on a tray made of stainless steel, and was allowed to cool andsolidify at room temperature. The cooled resin composition waspelletized to produce pellets of the resin composition. The resincomposition pellets obtained were subjected to the adhesion strengthmeasurement to measure the adhesion strength thereof. The results of theadhesion strength measurement are shown in Table 7.

Examples 3-2 to 3-32

Resin compositions of Examples 3-2 to 3-32 were produced in the samemanner as in Example 3-1, except that the kind of thepolar-group-containing olefin copolymer and the proportion of thepolar-group-containing olefin copolymer to the linear low-densitypolyethylene were changed. The proportions of the feed resins and theresults of the adhesion strength measurement are shown in Table 7 andTable 8.

Example 3-33

The polar-group-containing olefin copolymer (A′-3-7) was dry-blended inan amount of 3.0 g with 7.0 g of linear low-density polyethylene (tradename: F30FG, manufactured by Japan Polyethylene Corp.). This mixture wasintroduced into a compact twin-screw kneader (Type: MC15, manufacturedby DSM Xplore) and melt-kneaded for 5 minutes. For this kneading, thebarrel temperature and the screw rotation speed were set at 180° C. and100 rpm, respectively. After the 5 minutes, a rod-shaped resincomposition was extruded through the resin discharge port. This resincomposition was placed on a tray made of stainless steel, and wasallowed to cool and solidify at room temperature. The cooled resincomposition was pelletized to produce pellets of the resin composition.The resin composition pellets obtained were subjected to the adhesionstrength measurement to measure the adhesion strength thereof. Theresults of the adhesion strength measurement are shown in Table 10.

Example 3-34

The polar-group-containing olefin copolymer (A′-3-8) was dry-blended inan amount of 3.0 g with 7.0 g of linear low-density polyethylene (tradename: F30FG, manufactured by Japan Polyethylene Corp.). This mixture wasintroduced into a compact twin-screw kneader (Type: MC15, manufacturedby DSM Xplore) and melt-kneaded for 5 minutes. For this kneading, thebarrel temperature and the screw rotation speed were set at 180° C. and100 rpm, respectively. After the 5 minutes, a rod-shaped resincomposition was extruded through the resin discharge port. This resincomposition was placed on a tray made of stainless steel, and wasallowed to cool and solidify at room temperature. The cooled resincomposition was pelletized to produce pellets of the resin composition.The resin composition pellets obtained were subjected to the adhesionstrength measurement to measure the adhesion strength thereof. Theresults of the adhesion strength measurement are shown in Table 10.

Example 3-35 to Example 3-39

Resin compositions of Examples 3-35 to 3-39 were produced and examinedfor adhesion strength in the same manners as in Example 3-34, exceptthat the linear low-density polyethylene used in Example 3-34 wasreplaced with each of the olefin-based resins shown in Table 9. Themanufacturer, trade name, grade, polymerized monomers, and resinproperties of each of the olefin-based resins are shown in Table 9, andthe results of the adhesion strength measurement are shown in Table 10.Each “LLDPE” in Table 9 indicates linear low-density polyethylene.

Comparative Example 3-1 to Comparative Example 3-10

Resin compositions of Comparative Example 3-1 to Comparative Example3-10 were produced in the same manner as in Example 3-1, except that thekind of the polar-group-containing olefin copolymer was changed to thepolar-group-containing olefin copolymer (A′-3-9) and that the proportionof the polar-group-containing olefin copolymer to the linear low-densitypolyethylene was changed. The proportions of the feed resins and theresults of the adhesion strength measurement are shown in Table 11.

Comparative Example 3-11

Linear low-density polyethylene (trade name: Novatec (F30FG) (referredto as “LLDPE” in the table), manufactured by Japan Polyethylene Corp.)was introduced in an amount of 10 g into a compact twin-screw kneader(Type: MC15, manufactured by DSM Xplore) and melt-kneaded for 5 minutes.For this kneading, the barrel temperature and the screw rotation speedwere set at 180° C. and 100 rpm, respectively. After the 5 minutes, arod-shaped resin composition was extruded through the resin dischargeport. This resin composition was placed on a tray made of stainlesssteel, and was allowed to cool and solidify at room temperature. Thecooled resin composition was pelletized to produce pellets of the resincomposition. The resin composition pellets obtained were subjected tothe adhesion strength measurement to measure the adhesion strengththereof. The results of the adhesion strength measurement are shown inTable 11.

TABLE 7 Proportion of each resin Proportion of each resin Proportion ofeach resin Adhesion in resin composition in resin composition in resincomposition strength (wt %) (parts by weight) (feed amount (g)) (gf/10mm) A′-3-1 A′-3-2 LLDPE A′-3-1 A′-3-2 LLDPE A′-3-1 A′-3-2 LLDPEAdherend: PA Example 3-1 0.5 99.5 100 19900 0.05 9.95 2625 Example 3-2 199 100 9900 0.1 9.9 4150 Example 3-3 5 95 100 1900 0.5 9.5 4050 Example3-4 10 90 100 900 1 9 5000 Example 3-5 20 80 100 400 2 8 5000 Example3-6 30 70 100 233 3 7 3100 Example 3-7 99 1 100 1 9.9 0.1 4000 Example3-8 1 99 100 9900 0.1 9.9 875 Example 3-9 5 95 100 1900 0.5 9.5 1763Example 3-10 10 90 100 900 1 9 1230 Example 3-11 25 75 100 300 2.5 7.51100 Example 3-12 50 50 100 100 5 5 875 Example 3-13 70 30 100 43 7 31100 Example 3-14 85 15 100 18 8.5 1.5 1150 Example 3-15 99 1 100 1 9.90.1 950

TABLE 8 Proportion of each resin in resin Proportion of each resin inresin composition composition (wt %) (parts by weight) A′-3-3 A′-3-4A′-3-5 A′-3-6 LLDPE A′-3-3 A′-3-4 A′-3-5 A′-3-6 LLDPE Example 1 99 1009900 3-16 Example 5 95 100 1900 3-17 Example 10 90 100 900.0 3-18Example 20 80 100 400.0 3-19 Example 30 70 100 233.3 3-20 Example 50 50100 100.0 3-21 Example 70 30 100 42.9 3-22 Example 99 1 100 1.0 3-23Example 20 80 100 400.0 3-24 Example 40 60 100 150.0 3-25 Example 60 40100 66.7 3-26 Example 80 20 100 25.0 3-27 Example 99 1 100 1.0 3-28Example 30 70 100 233.3 3-29 Example 70 30 100 42.9 3-30 Example 99 1100 1.0 3-31 Example 30 70 3-32 Proportion of each resin in resinAdhesion strength composition (gf/10 mm) (feed amount (g)) Adherend:Adherend: A′-3-3 A′-3-4 A′-3-5 A′-3-6 LLDPE polyimide fluororesinExample 0.1 9.9 1950 ND 3-16 Example 0.5 9.5 975 ND 3-17 Example 1.0 9.0850 ND 3-18 Example 2.0 8.0 800 ND 3-19 Example 3.0 7.0 750 ND 3-20Example 5.0 5.0 825 ND 3-21 Example 7.0 3.0 800 ND 3-22 Example 9.9 0.11125 ND 3-23 Example 2.0 8.0 ND 2275 3-24 Example 4.0 6.0 ND 4171 3-25Example 6.0 4.0 ND 3900 3-26 Example 8.0 2.0 ND 3317 3-27 Example 9.90.1 ND 3200 3-28 Example 3.0 7.0 245 ND 3-29 Example 7.0 3.0 700 ND 3-30Example 9.9 0.1 850 ND 3-31 Example 1788 ND 3-32

TABLE 9 MFR Density Grade Manufacturer Trade name Sort of resinComonomer 1 Comonomer 2 g/10 min g/cm³ F30FG Japan Polyethylene Corp.Novatec LLDPE ethylene 1-butene 1.0 0.921 UH411 Japan Polyethylene Corp.Novatec LLDPE ethylene 1-butene 0.3 0.924 SF720GN Japan PolyethyleneCorp. Novatec LLDPE ethylene 1-hexene 0.8 0.928 F30HG Japan PolyethyleneCorp. Novatec LLDPE ethylene 1-butene 2.1 0.920 Z50MG Japan PolyethyleneCorp. Novatec LLDPE ethylene 1-butene 9.0 0.925 US370GN JapanPolyethylene Corp. Novatec LLDPE ethylene 1-butene 16.0 0.921

TABLE 10 Proportion of each resin in resin composition Adhesion trength(parts by weight) (gf/10 mm) A′-3-7 A′-3-8 F30FG UH411 SF720GN F30HGZ50MG US270GN Adherend: polyamide Example 3-33 100 233 4480 Example 3-34100 233 5020 Example 3-35 100 233 4075 Example 3-36 100 233 4200 Example3-37 100 233 4830 Example 3-38 100 233 3500 Example 3-39 100 233 3810

TABLE 11 Proportion Proportion of of each Proportion of each resin resinin resin each resin in resin composition in resin Adhesion strengthcomposition (parts composition (gf/10 mm) (wt %) by weight) (feed amount(g)) Adherend: A′-3-9 LLDPE A′-3-9 LLDPE A′-3-9 LLDPE Adherend: PA EFEPComparative 10 90 100 900 1.0 9.0 225 ND Example 3-1 Comparative 20 80100 400 2.0 8.0 85 808 Example 3-2 Comparative 30 70 100 233 3.0 7.0 55ND Example 3-3 Comparative 40 60 100 150 4.0 6.0 ND 867 Example 3-4Comparative 50 50 100 100 5.0 5.0 225 ND Example 3-5 Comparative 60 40100 66.7 6.0 4.0 ND 758 Example 3-6 Comparative 70 30 100 42.9 7.0 3.0600 ND Example 3-7 Comparative 80 20 100 25.0 8.0 2.0 ND 1771 Example3-8 Comparative 85 15 100 17.6 8.5 1.5 790 ND Example 3-9 Comparative 991 100 1.0 9.9 0.1 3850 2783 Example 3-10 Comparative 0 100 0 — 0 10 0 0Example 3-11

Discussion on the Results of the Examples and Comparative Examples

Examples 3-1 to 3-7 are resin compositions obtained by compounding 100parts by weight of the polar-group-containing olefin copolymer (A′-3-1)with linear low-density polyethylene (LLDPE) in respective proportions.A relationship between the proportion of the polar-group-containingolefin copolymer (A′-3-1) and the strength of adhesion to the polyamideis shown in FIG. 4.

Comparative Examples 3-1, 3-2, 3-3, 3-5, 3-7, 3-9, and 3-10 are resincompositions obtained by compounding 100 parts by weight of thepolar-group-containing olefin copolymer (A′-3-9), which had beenproduced by a high-pressure process, with linear low-densitypolyethylene (LLDPE) in respective proportions. A relationship betweenthe proportion of the polar-group-containing olefin copolymer (A′-3-9)and the strength of adhesion to the polyamide is shown in FIG. 5. Theresin compositions into which the polar-group-containing olefincopolymer (A′-3-9) has been incorporated show sufficient adhesiveness inthe region where the proportion of the polar-group-containing olefincopolymer (A′-3-9) is large, but the adhesiveness decreases abruptly asthe proportion thereof decreases. Meanwhile, the resin compositions intowhich the polar-group-containing olefin copolymer (A′-3-1) has beenincorporated retain high adhesiveness regardless of the proportion ofthe polar-group-containing olefin copolymer (A′-3-1). These resultsdemonstrated that resin compositions obtained by blending thepolar-group-containing olefin copolymer produced in the presence of atransition metal catalyst with an olefin-based resin in proportionswithin a specific range show sufficient adhesiveness to highly polarmaterials even when the proportion of the olefin-based resin isincreased.

Example 3-1 to Example 3-23 and Example 3-29 to Example 3-32 are resincompositions obtained by compounding 100 parts by weight of each ofpolar-group-containing olefin copolymers differing inpolar-group-content (A′-3-1, A′-3-2, A′-3-3, A′-3-5, and A′-3-6) withLLDPE in various proportions. A relationship between the proportion ofthe polar-group-containing olefin copolymer (A′-3-2) and the strength ofadhesion to the polyamide is shown in FIG. 6, a relationship between theproportion of the polar-group-containing olefin copolymer (A′-3-3) andthe strength of adhesion to the polyamide is shown in FIG. 7, and arelationship between the proportion of the polar-group-containing olefincopolymer (A′-3-5) and the strength of adhesion to the polyamide isshown in FIG. 8. These resin compositions show sufficient adhesivenessregardless of the proportion of each polar-group-containing olefincopolymer. This fact has made it clear that the resin compositionaccording to the invention exhibits sufficient adhesiveness even whenthe amount of polar-group structural units contained in the incorporatedpolar-group-containing olefin copolymer is any of those values.

Example 3-33 to Example 3-39 are compositions obtained by compounding100 parts by weight of a polar-group-containing olefin copolymer with233 parts by weight of any of various olefin-based resins. Theolefin-based resin compositions obtained each show sufficientadhesiveness to the polyamide regardless of the MFR and density of theolefin resin and the kinds of the monomers polymerized. This fact showsthat olefin-based resins, regardless of the kinds and propertiesthereof, exhibit sufficient adhesiveness so long as these olefin-basedresins have been blended with any of the polar-group-containing olefincopolymers in a proportion within a specific range.

Examples 3-24 to 3-28 are resin compositions obtained by compounding 100parts by weight of the polar-group-containing olefin copolymer (A′-3-4)with linear low-density polyethylene (LLDPE) in respective proportions.A relationship between the proportion of the polar-group-containingolefin copolymer (A′-3-4) and the strength of adhesion to thefluororesin is shown in FIG. 9. Comparative Examples 3-2, 3-4, 3-6, 3-8,and 3-10 are resin compositions obtained by compounding 100 parts byweight of the polar-group-containing olefin copolymer (A′-3-9), whichhad been produced by a high-pressure process, with linear low-densitypolyethylene (LLDPE) in respective proportions. A relationship betweenthe proportion of the polar-group-containing olefin copolymer (A′-3-9)and the strength of adhesion to the fluororesin is shown in FIG. 10. Theresin compositions into which the polar-group-containing olefincopolymer (A′-3-9) has been incorporated show sufficient adhesiveness inthe region where the proportion of the polar-group-containing olefincopolymer (A′-3-9) is large, but the adhesiveness decreases abruptly asthe proportion thereof decreases. Meanwhile, the resin compositions intowhich the polar-group-containing olefin copolymer (A′-3-4) has beenincorporated retain high adhesiveness regardless of the proportion ofthe polar-group-containing olefin copolymer (A′-3-4). This factdemonstrated that resin compositions obtained by blending thepolar-group-containing olefin copolymer produced in the presence of atransition metal catalyst with an olefin-based resin in proportionswithin a specific range show sufficient adhesiveness to highly polarmaterials even when the proportion of the olefin-based resin isincreased, and that this tendency is not limited to combinations with aspecific highly polar base.

The reason why the olefin-based resin compositions obtained by blendinga polar-group-containing olefin copolymer having a linear structure withan olefin-based resin retain adhesiveness regardless of the proportionof the polar-group-containing olefin copolymer to the olefin-based resinis not clear. It is, however, thought that the polar-group-containingolefin copolymer contained in each olefin-based resin compositionprobably needs to have a linear molecular structure. The adhesiveness ofan olefin copolymer to highly polar materials of different kinds isevaluated in terms of numerical values measured in a peel test such asthat shown in JIS K6854, 1-4 (1999) “Adhesives—Peel Adhesion StrengthTest Method”. It is, however, thought that such a numerical valuemeasured by this method is the sum of the chemical and physical bondingpower exerted at the interface between the different materials and thecohesive power or stress for deformation of each material. Thepolar-group-containing olefin copolymer produced by a high-pressureradical polymerization process has a highly branched molecular structurewhich contains short-chain branches and long-chain branches in too largean amount. It is known that olefin-based resins having such a structureare inferior in mechanical property, cohesive power, impact resistance,etc. to olefin-based resins having a linear structure, and it ispresumed that polar-group-containing olefin copolymers also have thistendency. It is thought that even when a polar-group-containing olefincopolymer produced by a high-pressure radical polymerization process hassufficient chemical bonds with materials of different kinds, thecohesive power thereof is poorer than that of polar-group-containingolefin copolymers having a linear structure, resulting in a decrease inadhesiveness.

Experiment Example 4 Evaluation of Olefin-Based Resin Compositions (D′)(1) Amount of Polar-Group-Containing Structural Units inPolar-Group-Containing Olefin Copolymer (A′)

The amount of polar-group-containing structural units was determinedusing a ¹H-NMR spectrum. Specifically, the amount thereof was determinedby the method described in Experiment Example 1 and hereinabove.

(2) Weight-Average Molecular Weight (Mw) and Molecular-WeightDistribution Parameter (Mw/Mn)

Weight-average molecular weight (Mw) was determined by gel permeationchromatography (GPC). Molecular-weight distribution parameter (Mw/Mn)was determined by further determining the number-average molecularweight (Mn) by gel permeation chromatography (GPC) and calculating theratio between Mw and Mn, i.e., Mw/Mn. Specifically, the molecular weightand the parameter were determined by the method described in ExperimentExample 1 and hereinabove.

(3) Melting Point

Melting point is expressed by the peak temperature in an endothermiccurve determined with a differential scanning calorimeter (DSC). Themeasurement was made through the same steps as in Experiment Example 1.

(4) Adhesion Strength

Adhesion strength was measured by preparing both a pressed plate of atest sample and various base films, stacking and hot-pressing thepressed plate and each of the base films to thereby produce a layeredproduct, and subjecting the layered product to a peel test. Themeasurement was made through the same steps as in Experiment Example 1.

(5) Determination of δ(G*=0.1 MPa) by Dynamic ViscoelasticityMeasurement

δ(G*=0.1 MPa) was determined by a dynamic viscoelasticity measurementthrough the same steps as in Experiment Example 1.

(6) Amount of Aluminum (Al)

The amount of the aluminum (Al) contained in the polar-group-containingolefin copolymer (A′) was determined through the same steps as inExperiment Example 1.

(7) Heat of Fusion ΔH

Heat of fusion ΔH (J/g) was determined using a differential scanningcalorimeter (DSC) under the same conditions as in the measurement ofmelting point. A detailed explanation was given hereinabove.

(8) Melt Flow Rate (MFR)

MFR was measured through the same steps as in Experiment Example 3.

(9) Density

Density was determined through the same steps as in Experiment Example3.

Production Example 4-1 Production of Polar-Group-Containing OlefinCopolymer (A′-4-1) Synthesis of Drent Type Ligand(2-Isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)

Drent type ligand(2-isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)was obtained in the same manner as in Example 1-1.

Formation of Complex

Into a 30-mL flask which had undergone sufficient nitrogen displacementwere introduced 100 μmol of palladium bisdibenzylideneacetone and 100μmol of the phosphorus-sulfonic acid ligand (I). Dehydrated toluene (10mL) was added thereto. Thereafter, this mixture was treated with anultrasonic vibrator for 10 minutes to thereby prepare a catalyst slurry.

Copolymerization of Ethylene with 4-Vinyl-1,2-epoxycyclohexane

Copolymerization of ethylene with 4-vinyl-1,2-epoxycyclohexane wasconducted in the same manner as in Example 1-2.

The conditions and results of the polymerization are shown in Table 12,and the results of the property examinations are shown in Table 13.

Production Example 4-2 Production of Polar-Group-Containing OlefinCopolymer (A′-4-2) Synthesis of SHOP Type Ligand (B-27DM)

A SHOP type ligand (B-27DM) was synthesized in the same manner as inExample 1-4.

Formation of Complex

A product of reaction between the B-27DM and Ni(COD)2 was obtained inthe same manner as in Example 1-4.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 54.9 mg (0.15 mmol) oftri-n-octylaluminum (TNOA), and 2.7 mL (15 mmol) of 4-HBAGE. Whilestirring the contents, the autoclave was heated to 105° C. and nitrogenwas supplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of2.8 MPa so as to result in a partial ethylene pressure of 2.5 MPa. Afterthe temperature and the pressure had become stable, 3.0 mL (30 μmol) ofthe B-27DM-Ni complex solution prepared above was forced into theautoclave with nitrogen to initiate copolymerization. During thereaction, the temperature was kept at 105° C. and ethylene wascontinuously fed so as to maintain the pressure. The monomers werepolymerized for 60 minutes. Thereafter, the autoclave was cooled anddepressurized to terminate the reaction. The reaction solution waspoured into 1 L of acetone to precipitate a polymer. The resultantpolymer was recovered through filtration and washing and then dried at60° C. under vacuum until a constant weight was reached. Thus, thepolar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 38 g. The conditions and results of the polymerization areshown in Table 12, and the results of the property examinations areshown in Table 13. In Table 12, the polymerization activity indicatesthe amount (g) of the copolymer yielded per mol of the complex used forthe polymerization. Incidentally, the polymerization activity wascalculated on the assumption that the B-27DM and the Ni(COD)2 hadreacted in a ratio of 1:1 to form the nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Production Example 4-4 to Production Example 4-7 Production ofPolar-Group-Containing Olefin Copolymers (A′-4-4 to A′-4-7)

Polar-group-containing olefin copolymers of Production Example 4-4 toProduction Example 4-7 were prepared by conducting polymerization in thesame manner as in Production Example 4-2, except that the amount of theligand, concentration of the polar-group-containing monomer,polymerization temperature, and polymerization period were changed. Theconditions and results of the polymerization are shown in Table 12, andthe results of the property examinations are shown in Table 13.

Production Example 4-3 and Production Example 4-8 Production ofPolar-Group-Containing Olefin Copolymers (A′-4-3 and A′-4-8)

Polymerization was conducted basically in the same manner as inProduction Example 4-2, except that the ethylene replenishment afterinitiation of the polymerization was omitted. The amount of the ligand,concentration of the polar-group-containing monomer, polymerizationtemperature, and polymerization period were changed in performing thepolymerization. Thus, polar-group-containing olefin copolymers ofProduction Example 4-3 and Production Example 4-8 were prepared. Theconditions and results of the polymerization are shown in Table 12, andthe results of the property examinations are shown in Table 13. In thispolymerization method, the partial ethylene pressure at the time oftermination of the polymerization is lower than that at the time of thepolymerization initiation because ethylene replenishment is omitted.

Polar-Group-Containing Olefin Copolymer (A′-4-9)

This copolymer is a polar-group-containing olefin copolymer (trade name.Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.) which is acopolymer of ethylene with glycidyl methacrylate and was produced by ahigh-pressure process. The results of the property examinations areshown in Table 13.

Polar-Group-Containing Olefin Copolymer (A′-4-10)

This copolymer is a polar-group-containing olefin copolymer (trade name:Bondfast 2C, manufactured by Sumitomo Chemical Co., Ltd.) which is acopolymer of ethylene with glycidyl methacrylate and was produced by ahigh-pressure process. The results of the property examinations areshown in Table 13.

TABLE 12 Amount of polar- Polymerization conditions Amount group-Parital of containing ethylene Amount Catalytic Kind of ligand TNOA Kindof polar-group- monomer pressure Temperature Period yielded efficiencyRun ligand μmol mmol containing monomer mmol mL MPa ° C. min g g/molProduction I 50 — 1,2-epoxy-4- 200 20.9 2.0 100 240 85 1.7E+06 Examplevinylcyclohexane 4-1 Production B27DM 30 0.15 4-hydroxybutyl acrylate 152.7 2.5 105 60 38 1.3E+06 Example glycidylether 4-2 Production B27DM 250.15 4-hydroxybutyl acrylate 15 2.7 2.0→1.0 105 170 33 1.3E+06 Exampleglycidylether 4-3 Production B27DM 20 0.10 4-hydroxybutyl acrylate 152.7 2.5 90 50 41 2.0E+06 Example glycidylether 4-4 Production B27DM 3800.40 4-hydroxybutyl acrylate 50 9.1 2.0 90 120 60 1.6E+05 Exampleglycidylether 4-5 Production B27DM 100 0.20 4-hydroxybutyl acrylate 509.1 2.0 90 304 49 4.9E+05 Example glycidylether 4-6 Production B27DM 2000.20 4-hydroxybutyl acrylate 50 9.1 2.0 90 152 40 2.0E+05 Exampleglycidylether 4-7 Production B27DM 140 0.10 4-hydroxybutyl acrylate 509.1 2.0→1.5 90 130 17 1.2E+05 Example glycidylether 4-8

TABLE 13 Amount of residual aluminum Amount Calculated Weight-Molecular- of polar- from amount of Determined average weight groupalkylaluminum by fluorescent molecular distribution Melting δ strucuraladded for X-ray Kind of polar-group- weight parameter point (G* = 0.1MPa) unit polymerization analysis Run Name containing monomer Mw * 10⁻⁴Mw/Mn ° C. ° mol % μg_(Al)/g μg_(Al)/g Production A′-4-1 1,2-epoxy-4-10.0 2.04 130.9 63.3 0.08 0 ND Example vinylcyclohexane 4-1 ProductionA′-4-2 4-hydroxybutyl acrylate 7.0 2.09 122.3 ND 0.82 107 ND Exampleglycidylether 4-2 Production A′-4-3 4-hydroxybutyl acrylate 5.8 2.09120.6 60.3 0.98 121.9 130.0 Example glycidylether 4-3 Production A′-4-44-hydroxybutyl acrylate 13.1 2.35 122.4 ND 1.04 66.0 ND Exampleglycidylether 4-4 Production A′-4-5 4-hydroxybutyl acrylate 11.2 2.46119.2 48.7 2.22 180 171 Example glycidylether 4-5 Production A′-4-64-hydroxybutyl acrylate 9.2 2.24 112.4 49.2 2.45 111 ND Exampleglycidylether 4-6 Production A′-4-7 4-hydroxybutyl acrylate 8.2 2.45112.4 50 3.23 135 ND Example glycidylether 4-7 Production A′-4-84-hydroxybutyl acrylate 3.2 2.18 96.7 ND 5.31 157 ND Exampleglycidylether 4-8 — A′-4-9 glycidyl methacrylate 10.6 5.17 99.2 37.32.99 0 ND — A′-4-10 glycidyl methacrylate 12.0 5.92 105.5 36.2 1.43 0 ND

Example 4-1

The polar-group-containing olefin copolymer (A′-4-1) was dry-blended inan amount of 7.0 g with 3.0 g of high-density polyethylene (trade name:HS330P, manufactured by Japan Polyethylene Corp.) as an olefin-basedresin. This mixture was introduced into a compact twin-screw kneader(Type: MC15, manufactured by DSM Xplore) and melt-kneaded for 5 minutes.For this kneading, the barrel temperature and the screw rotation speedwere set at 180° C. and 100 rpm, respectively. After the 5 minutes, arod-shaped olefin-based resin composition was extruded through the resindischarge port. This olefin-based resin composition was placed on a traymade of stainless steel, and was allowed to cool and solidify at roomtemperature. The cooled olefin-based resin composition was pelletized toproduce pellets of the olefin-based resin composition, which weresubjected to tests for examining various properties. The manufacturer,grade, trade name, sort, polymerized monomers, and resin properties ofthe polyethylene used are shown in Table 14, and the proportion thereofin the olefin-based resin composition is shown in Table 15. The resultsof the property evaluation are shown in Table 16.

In Table 14, “HDPE” indicates high-density polyethylene, “LLDPE”indicates linear low-density polyethylene, “PP” indicates polypropylene,and “COC” indicates cycloolefin copolymer.

Example 4-2 to Example 4-12 and Comparative Example 4-1 to ComparativeExample 4-4

Resin compositions of Example 4-2 to Example 4-12 and ComparativeExample 4-1 to Comparative Example 4-4 were produced in the same manneras in Example 4-1, except that the kind of the polar-group-containingolefin copolymer, the kind of the olefin-based resin, and the proportionwere changed. The manufacturer, grade, trade name, sort, polymerizedmonomers, and resin properties of each olefin-based resin are shown inTable 14, and the proportions of the feed resins are shown in Table 15.The results of the property evaluation are shown in Table 16.

TABLE 14 Melting Trade MFR Density point Grade Manufacturer name Sort ofresin Comonomer 1 Comonomer 2 g/10 min g/cm³ ° C. 8007F-500 PolyplasticsCo., TOPAS COC ethylene norbornene 2.0 0.995 — Ltd HB530RN JapanPolyethylene Novatec HDPE ethylene 1-butene 0.7 0.960 135.0 Corp. HS330PJapan Polyethylene Novatec HDPE ethylene 1-butene 0.4 0.945 134.0 Corp.UF943 Japan Polyethylene Novatec LLDPE ethylene 1-butene 2.3 0.933 125.0Corp. F30FG Japan Polyethylene Novatec LLDPE ethylene 1-butene 1.0 0.921121.6 Corp. NF444N Japan Polyethylene Harmorex LLDPE ethylene 1-hexene2.0 0.912 121.0 Corp. UE130G Japan Polyethylene Novatec LLDPE ethylene1-butene 1.0 0.905 116.2 Corp. WFX4TA Japan Polypropylene Wintec PPpropylene — 7.0 0.896 123.7 Corp. A-4085S Mitsui Chemicals Tafmerethylene/butene ethylene 1-butene 3.6 0.885 69.5 Inc. copolymer

TABLE 15 Com- Com- Com- Com- par- par- par- par- Ex- Ex- Ex- Ex- Ex- Ex-Ex- Ex- Ex- Ex- Ex- Ex- ative ative ative ative am- am- am- am- am- am-am- am- am- am- am- am- Exam- Exam- Exam- Exam- ple ple ple ple ple pleple ple ple ple ple ple ple ple ple ple 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-84-9 4-10 4-11 4-12 4-1 4-2 4-3 4-4 Proportion A′-4-1 100 of each A′-4-2100 resin A′-4-3 100 100 100 100 in A′-4-4 100 100 resin A′-4-5 100 100composition A′-4-6 100 (parts A′-4-7 100 100 by A′-4-8 100 weight)A′-4-9 100 A′-4-10 100 8007F-500 400 HB530RN 233 233 233 HS330P 43 233233 UF943 300 F30FG 233 300 300 NF444N 400 UE130G 186 WFX4TA 400 A-4085S233 233

TABLE 16 Proportion of polar- Heat of group- Melting fusion containingPolar-group- Density Strength Strength point ΔH of olefin containing ofolefin- of adhesion of adhesion of resin resin copolymer olefinOlefin-based based resin to PA to EFEP composition composition wt %copolymer resin g/cm³ gf/10 mm gf/10 mm ° C. J/g Example 4-1 70 A′-4-1HS330P 0.945 155 ND 132.1 209 Example 4-2 30 A′-4-2 HS330P 0.945 2875 ND131.2 202 Example 4-3 20 A′-4-3 WFX4TA 0.896 111 ND 120.6 87 Example 4-420 A′-4-3 8007F-500 0.995 140 ND 120.0 37 Example 4-5 25 A′-4-3 UF9430.933 2530 ND 124.0 158 Example 4-6 20 A′-4-3 NF444N 0.912 2600 ND 120.8161 Example 4-7 35 A′-4-4 UE130G 0.905 4050 ND 120.1 105 Example 4-8 30A′-4-5 F30FG 0.921 1320 208 120.6 125 Example 4-9 30 A′-4-6 HS330P 0.9451750 ND 132.5 185 Example 4-10 30 A′-4-7 HB530RN 0.960 400 ND 132.3 198Example 4-11 25 A′-4-7 F30FG 0.921 730 172 120.4 117 Example 4-12 20A′-4-8 F30FG 0.921 510 154 120.5 115 Comparative 30 A′-4-4 A-4085S 0.8853300 1540 118.8 45 Example 4-1 Comparative 30 A′-4-5 A-4085S 0.885 3250ND 115.5 37 Example 4-2 Comparative 30 A′-4-9 HB530RN 0.960 15 48 133.7186 Example 4-3 Comparative 30 A′-4-10 HB530RN 0.960 43 36 132.5 194Example 4-4

Discussion on the Results of the Examples and Comparative Examples

Example 4-1 to Example 4-12 are olefin-based resin compositions obtainedby suitably blending 100 parts by weight each of polar-group-containingolefin copolymers (A′-4-1, A′-4-2, A′-4-3, A′-4-4, A′-4-5, A′-4-6,A′-4-7, and A′-4-8) with 1-99,900 parts by weight of any of olefin-basedresins having a density of 0.890 g/cm³ or higher, and show sufficientadhesiveness to the polyamide. These resin compositions further have amelting point of 119° C. or above and show satisfactorily high heatresistance. Moreover, Example 4-1 to Example 4-3 and Example 4-5 toExample 4-12, in which olefin-based resins having a melting point of 90°C. or higher had been blended, showed higher heat resistance including amelting point of 119° C. or higher and a heat of fusion AH of 80 J/g orlarger.

Comparative Example 4-1 and Comparative Example 4-2, in which anolefin-based resin having a density lower than 0.890 g/cm³ is used, havea melting point lower than 119° C. to show poor heat resistance.Furthermore, these resin compositions have a heat of fusion ΔH less than80 J/g, showing that the heat resistance thereof is poorer.

Comparative Example 4-3 and Comparative Example 4-4 are olefin-basedresin compositions obtained by suitably blending 100 parts by weighteach of polar-group-containing olefin copolymers likewise produced by ahigh-pressure radical process (A′-4-9 and A′-4-10) with 1 to 99,900parts by weight of an olefin-based resin having a density of 0.890 g/cm³or higher, and showed exceedingly low adhesiveness to the polyamidealthough satisfactory in terms of heat resistance. This fact showed thatthe polar-group-containing olefin copolymer of the invention decreaseslittle in adhesiveness when blended with an olefin-based resin having adensity of 0.890 g/cm³ or higher, as compared withpolar-group-containing olefin copolymers produced by a high-pressureradical polymerization process, and that so long as 100 parts by weightof the polar-group-containing olefin copolymer according to theinvention is blended with 1 to 99,900 parts by weight of an olefin-basedresin having a density of 0.890 g/cm³ or higher, it is possible tobalance adhesiveness with heat resistance.

The reason why the olefin-based resin compositions obtained by blendinga polar-group-containing olefin copolymer having a linear structure withan olefin-based resin having a density of 0.890 g/cm³ or higher haveundergone only a slight decrease in adhesiveness and have sufficientadhesiveness is not clear. It is, however, thought that thepolar-group-containing olefin copolymer contained in each olefin-basedresin composition probably needs to have a linear molecular structure.The adhesiveness of an olefin copolymer to highly polar materials ofdifferent kinds is evaluated in terms of numerical values measured in apeel test such as that shown in JIS K6854, 1-4 (1999) “Adhesives—PeelAdhesion Strength Test Method”. It is, however, thought that such anumerical value measured by this method is the sum of the chemical andphysical bonding power exerted at the interface between the differentmaterials and the cohesive power or stress for deformation of eachmaterial. The polar-group-containing olefin copolymer produced by ahigh-pressure radical polymerization process has a highly branchedmolecular structure which contains short-chain branches and long-chainbranches in too large an amount. It is known that olefin-based resinshaving such a structure are inferior in mechanical property, cohesivepower, impact resistance, etc. to olefin-based resins having a linearstructure, and it is presumed that polar-group-containing olefincopolymers also have this tendency. It is thought that even when apolar-group-containing olefin copolymer produced by a high-pressureradical polymerization process has sufficient chemical bonds withmaterials of different kinds, the cohesive power thereof is poorer thanthat of polar-group-containing olefin copolymers having a linearstructure, resulting in a decrease in adhesiveness.

Example 4-8, Example 4-11, and Example 4-12 are olefin-based resincompositions obtained by suitably blending 100 parts by weight each ofpolar-group-containing olefin copolymers with 1 to 99,900 parts byweight of an olefin-based resin having a density of 0.890 g/cm³ orhigher, and show sufficient adhesiveness even to the fluororesin. Thisfact has made it clear that materials to which the olefin-based resincomposition of the invention has adhesiveness are not limited to aspecific highly polar material, and the composition has sufficientadhesiveness to highly polar materials of various kinds.

Example 4-1 to Example 4-12 are compositions in which 100 parts byweight each of polar-group-containing olefin copolymers have beencompounded with any of olefin-based resins having a density of 0.890g/cm³ or higher. It was demonstrated that the olefin-based resincompositions obtained can have sufficient heat resistance balanced withhigh adhesiveness to highly polar resins, regardless of the MFR of theolefin-based resin, the kinds of the polymerized monomers, and theproportion. This fact shows that so long as the olefin-based resin to beincorporated into the polar-group-containing olefin copolymer of theinvention has a density of 0.890 g/cm³ or higher, it is possible tobalance the heat resistance of the olefin-based resin composition withthe adhesiveness thereof

Experiment Example 5 Evaluation of Olefin-Based Resin Compositions (D″)(1) Amount of Polar-Group-Containing Structural Units inPolar-Group-Containing Olefin Copolymer (A′)

The amount of polar-group-containing structural units was determinedusing a ¹H-NMR spectrum. Specifically, the amount thereof was determinedby the method described in Experiment Example 1 and hereinabove.

(2) Weight-Average Molecular Weight (Mw) and Molecular-WeightDistribution Parameter (Mw/Mn)

Weight-average molecular weight (Mw) was determined by gel permeationchromatography (GPC). Molecular-weight distribution parameter (Mw/Mn)was determined by further determining the number-average molecularweight (Mn) by gel permeation chromatography (GPC) and calculating theratio between Mw and Mn, i.e., Mw/Mn. Specifically, the molecular weightand the parameter were determined by the method described in ExperimentExample 1 and hereinabove.

(3) Melting Point

Melting point is expressed by the peak temperature in an endothermiccurve determined with a differential scanning calorimeter (DSC). Themeasurement was made through the same steps as in Experiment Example 1.

(4) Adhesion Strength

Adhesion strength was measured by preparing both a pressed plate of atest sample and various base films, stacking and hot-pressing thepressed plate and each of the base films to thereby produce a layeredproduct, and subjecting the layered product to a peel test. Themeasurement was made through the same steps as in Experiment Example 1.

(5) Adhesion Strength Ratio

The adhesion strength of each of the resin compositions of the Examplesand Comparative Examples and that of the polar-group-containing olefincopolymer contained in the resin composition were measured by the methodfor measuring adhesion strength, and the adhesion strength of the resincomposition was divided by the adhesion strength of thepolar-group-containing olefin copolymer contained in the resincomposition, the resultant value being taken as adhesion strength ratio.

This value is an index to the effect of improving adhesiveness byblending a polar-group-containing olefin copolymer with an olefin-basedresin; in cases when this value is larger than “1”, this means that theadhesiveness has been improved by blending the polar-group-containingolefin copolymer with the olefin-based resin.

(6) Determination of δ(G*=0.1 MPa) by Dynamic ViscoelasticityMeasurement

δ(G*=0.1 MPa) was determined by a dynamic viscoelasticity measurementthrough the same steps as in Experiment Example 1.

(7) Amount of Aluminum (Al)

The amount of the aluminum (Al) contained in the polar-group-containingolefin copolymer (A′) was determined through the same steps as inExperiment Example 1.

(8) Melt Flow Rate (MFR)

MFR was measured through the same steps as in Experiment Example 3.

(9) Density

Density was determined through the same steps as in Experiment Example3.

Production Example 5-1 Production of Polar-Group-Containing OlefinCopolymer (A′-5-1) Synthesis of Drent Type Ligand(2-Isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)

Drent type ligand(2-isopropylphenyl)(2′-methoxyphenyl)(2″-sulfonylphynyl)phosphine (I)was obtained in the same manner as in Example 1-1.

Formation of Complex

Into a 30-mL flask which had undergone sufficient nitrogen displacementwere introduced 100 μmol of palladium bisdibenzylideneacetone and 100μmol of the phosphorus-sulfonic acid ligand (I). Dehydrated toluene (10mL) was added thereto. Thereafter, this mixture was treated with anultrasonic vibrator for 10 minutes to thereby prepare a catalyst slurry.

Copolymerization of Ethylene with 4-Vinyl-1,2-epoxycyclohexane

The atmosphere within an autoclave having a capacity of 2.4 L andequipped with stirring blades was replaced with purified nitrogen.Thereafter, dry toluene (1.0 L) and 20.9 mL (0.2 mol) of4-vinyl-1,2-epoxycyclohexane were introduced thereinto. While stirringthe contents, the autoclave was heated to 100° C. and nitrogen wassupplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of 2.3MPa so as to result in a partial ethylene pressure of 2 MPa. Aftercompletion of the pressure regulation, 50 μmol of the transition metalcomplex (I—Pd complex) was forced into the autoclave with nitrogen toinitiate copolymerization. During the reaction, the temperature was keptat 100° C. and ethylene was continuously fed so as to maintain thepressure. The monomers were thus polymerized for 240 minutes.Thereafter, the autoclave was cooled and depressurized to terminate thereaction. The reaction solution was poured into 1 L of acetone toprecipitate a polymer. The resultant polymer was recovered throughfiltration and washing and then dried at 60° C. under vacuum until aconstant weight was reached.

The conditions and results of the polymerization are shown in Table 17,and the results of the property examinations are shown in Table 18. InTable 17, the polymerization activity indicates the amount (g) of thecopolymer yielded per mol of the complex used for the polymerization.Incidentally, the polymerization activity was calculated on theassumption that the ligand and the palladium bisdibenzylideneacetone hadreacted in a ratio of 1:1 to form the palladium complex.

Production Example 5-2 Production of Polar-Group-Containing OlefinCopolymer (A′-5-2) Synthesis of SHOP Type Ligand2-(2,6-Diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyephenol(B-114)

2-(2,6-Diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114) was obtained in the same manner as in Example 1-16.

Formation of Complex

A solution of a complex of the2-(2,6-diphenoxyphenyl)(2-phenoxyphenyl)phosphanyl-6-(pentafluorophenyl)phenol(B-114) with bis-1,5-cyclooctadienenickel(0) (Ni(COD)2) was obtained inthe same manner as in Example 1-16.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

A copolymer of ethylene with 4-hydroxybutyl acrylate glycidyl ether(4-HBAGE) was obtained in the same manner as in Example 1-16.

The conditions and results of the polymerization are shown in Table 17,and the results of the property examinations are shown in Table 18.

Production Example 5-3 Production of Polar-Group-Containing OlefinCopolymer (A′-5-3) Synthesis of SHOP Type Ligand B-27DM

A SHOP type ligand (B-27DM) was synthesized in the same manner as inExample 1-4.

Formation of Complex

A product of reaction between the B-27DM and Ni(COD)2 was obtained inthe same manner as in Example 1-4.

Copolymerization of Ethylene with 4-Hydroxybutyl Acrylate Glycidyl Ether(4-HBAGE)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 36.6 mg (0.10 mmol) oftri-n-octylaluminum (TNOA), and 2.7 mL (15 mmol) of 4-HBAGE. Whilestirring the contents, the autoclave was heated to 105° C. and nitrogenwas supplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of2.8 MPa so as to result in a partial ethylene pressure of 2.5 MPa. Afterthe temperature and the pressure had become stable, 2.5 mL (25 mop ofthe B-27DM/Ni complex solution prepared above was forced into theautoclave with nitrogen to initiate copolymerization. During thereaction, the temperature was kept at 105° C. The monomers werepolymerized for 170 minutes. Thereafter, the autoclave was cooled anddepressurized to terminate the reaction. The reaction solution waspoured into 1 L of acetone to precipitate a polymer. The resultantpolymer was recovered through filtration and washing and then dried at60° C. under vacuum until a constant weight was reached. Thus, thepolar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 33 g.

The conditions and results of the polymerization are shown in Table 17,and the results of the property examinations are shown in Table 18. InTable 17, the polymerization activity indicates the amount (g) of thecopolymer yielded per mol of the complex used for the polymerization. Inthis polymerization method, the partial ethylene pressure at the time oftermination of the polymerization is lower than that at the time of thepolymerization initiation because ethylene replenishment is omitted.

Incidentally, the polymerization activity was calculated on theassumption that the B-27DM and the Ni(COD)2 had reacted in a ratio of1:1 to form the nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Production Example 5-4 Production of Polar-Group-Containing OlefinCopolymer (A′-5-4) Copolymerization of Ethylene with 4-HydroxybutylAcrylate Glycidyl Ether (4-HBAGE)

Into an autoclave having a capacity of 2.4 L and equipped with stirringblades were introduced 1,000 mL of dry toluene, 36.6 mg (0.10 mmol) oftri-n-octylaluminum (TNOA), and 2.7 mL (15 mmol) of 4-HBAGE. Whilestirring the contents, the autoclave was heated to 50° C. and nitrogenwas supplied to 0.3 MPa. Thereafter, ethylene was fed to a pressure of2.8 MPa so as to result in a partial ethylene pressure of 2.5 MPa. Afterthe temperature and the pressure had become stable, 2.0 mL (20 μmol) ofthe B-27DM-Ni complex solution prepared above was forced into theautoclave with nitrogen to initiate copolymerization. During thereaction, the temperature was kept at 50° C. and ethylene wascontinuously fed so as to maintain the pressure. The monomers werepolymerized for 50 minutes. Thereafter, the autoclave was cooled anddepressurized to terminate the reaction. The reaction solution waspoured into 1 L of acetone to precipitate a polymer. The resultantpolymer was recovered through filtration and washing and then dried at60° C. under vacuum until a constant weight was reached. Thus, thepolar-group-containing monomer which had remained in thepolar-group-containing copolymer was removed, and thepolar-group-containing olefin copolymer was finally recovered in anamount of 41 g.

The conditions and results of the polymerization are shown in Table 17,and the results of the property examinations are shown in Table 18. InTable 17, the polymerization activity indicates the amount (g) of thecopolymer yielded per mol of the complex used for the polymerization.

Incidentally, the polymerization activity was calculated on theassumption that the B-27DM and the Ni(COD)2 had reacted in a ratio of1:1 to form the nickel complex.

The 4-HBAGE subjected to the copolymerization was one which had beendehydrated with molecular sieve 3A.

Production Example 5-5 to Production Example 5-7 Production ofPolar-Group-Containing Olefin Copolymers (A′-5-5 to A′-5-7)

Polar-group-containing olefin copolymers of Production Example 5-5 toProduction Example 5-7 were prepared by conducting polymerization in thesame manner as in Production Example 5-4, except that the amount of theligand, concentration of the polar-group-containing monomer,polymerization temperature, and polymerization period were changed. Theconditions and results of the polymerization are shown in Table 17, andthe results of the property examinations are shown in Table 18.

Production Example 5-8 Production of Polar-Group-Containing OlefinCopolymer (A′-5-8)

A polar-group-containing olefin copolymer of Production Example 5-8 wasprepared by conducting polymerization in the same manner as inProduction Example 5-3, except that the amount of the ligand,concentration of the polar-group-containing monomer, polymerizationtemperature, and polymerization period were changed. The conditions andresults of the polymerization are shown in Table 17, and the results ofthe property examinations are shown in Table 18.

Polar-Group-Containing Olefin Copolymer (A′-5-9)

This copolymer is a polar-group-containing olefin copolymer (trade name:Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.) which is acopolymer of ethylene with glycidyl methacrylate and was produced by ahigh-pressure process. The results of the property examinations areshown in Table 18.

TABLE 17 Amount of Polymerization conditions Amount polar-group- Paritalof containing ethylene Amount Catalytic Kind of ligand TNOA Kind ofpolar-group- monomer pressure Temperature Period yielded efficiency Runligand μmol mmol containing monomer mmol mL MPa ° C. min g g/molProduction I 50 — 1,2-epoxy-4- 200 20.9 2.0 100 240 85 1.7E+06 Examplevinylcyclohexane 5-1 Production B114 20 0.10 4-hydroxybutyl acrylate 101.8 2.5→1.5 90 46 32 1.6E+06 Example glycidylether 5-2 Production B27DM25 0.15 4-hydroxybutyl acrylate 15 2.7 2.0→1.0 105 170 33 1.3E+06Example glycidylether 5-3 Production B27DM 20 0.10 4-hydroxybutylacrylate 15 2.7 2.5 90 50 41 2.0E+06 Example glycidylether 5-4Production B27DM 380 0.40 4-hydroxybutyl acrylate 50 9.1 2.0 90 120 601.6E+05 Example glycidylether 5-5 Production B27DM 200 0.204-hydroxybutyl acrylate 50 9.1 2.0 90 152 40 2.0E+05 Exampleglycidylether 5-6 Production B27DM 100 0.20 4-hydroxybutyl acrylate 509.1 2.0 90 251 35 3.5E+05 Example glycidylether 5-7 Production B27DM 1400.10 4-hydroxybutyl acrylate 50 9.1 2.0→1.5 90 130 17 1.2E+05 Exampleglycidylether 5-8

TABLE 18 Amount of residual aluminum Amount Calculated Weight-Molecular- of polar- from amount of Determined average weight groupalkylaluminum by fluorescent molecular distribution Melting δ strucuraladded for X-ray Kind of polar-group- weight parameter point (G* = 0.1MPa) unit polymerization analysis Run Name containing monomer Mw * 10⁻⁴Mw/Mn ° C. ° mol % μg_(Al)/g μg_(Al)/g Production A′-5-1 1,2-epoxy-4-10.0 2.04 130.9 63.3 0.08 0 ND Example vinylcyclohexane 5-1 ProductionA′-5-2 4-hydroxybutyl acrylate 2.8 2.35 127.8 ND 0.24 83.5 ND Exampleglycidylether 5-2 Production A′-5-3 4-hydroxybutyl acrylate 5.75 2.09120.6 60.3 0.98 121.9 130 Example glycidylether 5-3 Production A′-5-44-hydroxybutyl acrylate 13.1 2.35 122.4 ND 1.04 66.0 ND Exampleglycidylether 5-4 Production A′-5-5 4-hydroxybutyl acrylate 11.2 2.46119.2 48.7 2.22 180 171 Example glycidylether 5-5 Production A′-5-64-hydroxybutyl acrylate 8.2 2.45 112.4 50 3.23 136 ND Exampleglycidylether 5-6 Production A′-5-7 4-hydroxybutyl acrylate 7.3 2.49104.6 49.6 3.80 154 ND Example glycidylether 5-7 Production A′-5-84-hydroxybutyl acrylate 3.2 2.18 96.7 ND 5.31 157 ND Exampleglycidylether 5-8 — A′-5-9 glycidyl methacrylate 10.6 5.17 99.2 37.32.99 0 ND

Example 5-1

The polar-group-containing olefin copolymer (A′-5-1) was dry-blended inan amount of 7.0 g with 3.0 g of an ethylene/butene copolymer (tradename: Tafmer (A-4085S), manufactured by Mitsui Chemicals, Inc.). Thismixture was introduced into a compact twin-screw kneader (Type: MC15,manufactured by DSM Xplore) and melt-kneaded for 5 minutes. For thiskneading, the barrel temperature and the screw rotation speed were setat 180° C. and 100 rpm, respectively. After the 5 minutes, a rod-shapedresin composition was extruded through the resin discharge port. Thisresin composition was placed on a tray made of stainless steel, and wasallowed to cool and solidify at room temperature. The cooled resincomposition was pelletized to produce pellets of the olefin-based resincomposition. The olefin-based resin composition obtained was subjectedto tests for examining various properties. The manufacturer, grade,trade name, sort, polymerized monomers, and resin properties of theolefin-based resin used are shown in Table 19, and the proportionthereof in the olefin-based resin composition is shown in Table 20. Theresults of the property evaluation are shown in table 21.

In Table 19, “LDPE” indicates high-pressure-process low-densitypolyethylene, “LLDPE” indicates linear low-density polyethylene, “EEA”indicates ethylene/ethyl acrylate copolymer, “EVA” indicatesethylene/vinyl acetate copolymer, and “EPR” indicates ethylene/propylenerubber.

Example 5-2 to Example 5-12 and Comparative Example 5-1 to ComparativeExample 5-3

Resin compositions of Example 5-2 to Example 5-12 and ComparativeExample 5-1 to Comparative Example 5-3 were produced in the same manneras in Example 5-1, except that the kinds of the polar-group-containingolefin copolymer and olefin-based resin and the proportion of thepolar-group-containing olefin copolymer to the olefin-based resin werechanged. The manufacturer, grade, trade name, sort, polymerizedmonomers, and resin properties of each olefin-based resin used are shownin Table 19. The proportion thereof in the olefin-based resincomposition is shown in Table 20, and the results of the propertyevaluation are shown in Table 21.

TABLE 19 Melting Trade MFR Density point Grade Manufacturer name Sort ofresin Comonomer 1 Comonomer 2 g/10 min g/cm³ ° C. UF943 JapanPolyethylene Novatec LLDPE ethylene 1-butene 2.3 0.933 125.0 Corp. F30FGJapan Polyethylene Novatec LLDPE ethylene 1-butene 1.0 0.921 121.6 Corp.LF122 Japan Polyethylene Novatec LDPE ethylene — 0.3 0.923 110.7 Corp.KF370 Japan Polyethylene Kernel LLDPE ethylene 1-hexene 3.5 0.905 97.0Corp. A1150 Japan Polyethylene Rexpearl EEA ethylene ethyl 0.8 — 95.6Corp. acrylate LV440 Japan Polyethylene Novatec EVA ethylene vinyl 2.0 —89.1 Corp. acetate A-4085S Mitsui Chemicals Tafmer ethylene/buteneethylene 1-butene 3.6 0.885 69.5 Inc. copolymer KS430 Japan PolyethyleneKernel LLDPE ethylene 1-hexene 5.0 0.870 54.6 Corp. P-0280 MitsuiChemicals Tafmer EPR ethylene propylene 5.4 0.870 50.3 Inc. 8180 The DowChemical ENGAGE ethylene/octene ethylene 1-octene 0.5 0.863 49.6 Companycopolymer

TABLE 20 Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Compar- Compar-Compar- Exam- am- am am am am am am am am am am ative ative ative pleple ple ple ple ple ple ple ple ple ple ple Example Example Example 5-15-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 5-10 5-11 5-12 5-1 5-2 5-3 ProportionA′-5-1 100 of each A′-5-2 100 resin A′-5-3 100 100 100 in A′-5-4 100 100100 100 resin A′-5-5 100 composition A′-5-6 100 (parts A′-5-7 100 byA′-5-8 100 weight) A′-5-9 100 100 UF943 400 F30FG 233 233 LF122 400 233KF370 150 A1150 400 LV440 400 A-4085S 43 400 400 KS430 400 P-0280 4008180 400

TABLE 21 Proportion Strength of adhesion Strength of adhesion of polar-to PA to EFEP group- Melting Adhesion Adhesion containing Polar-group-point strength Adhesion strength Adhesion olefin containing of olefin-of resin strength of resin strength copolymer olefin Olefin-based basedresin composition ratio composition ratio wt % copolymer resin ° C.gf/10 mm times gf/10 mm times Example 5-1 70 A′-5-1 A-4085S 69.5 375 3.1Example 5-2 30 A′-5-2 F30FG 121.1 1670 25.7 Example 5-3 20 A′-5-3 LV44089.1 210 3.0 Example 5-4 20 A′-5-3 A1150 95.6 730 10.4 Example 5-5 20A′-5-4 P-0280 50.3 1142 114.2 Example 5-6 20 A′-5-4 A-4085S 69.5 1675167.5 Example 5-7 20 A′-5-4 KS430 54.6 617 61.7 Example 5-8 20 A′-5-48180 49.6 425 42.5 Example 5-9 20 A′-5-5 A-4085S 69.5 3400 3.6 Example5-10 20 A′-5-6 LF122 110.7 440 1.3 Example 5-11 40 A′-5-7 KF370 97.02230 2.0 Example 5-12 20 A′-5-8 F30FG 121.1 500 2.1 Comparative 20A′-5-3 UF943 125.0 65 0.93 Example 5-1 Comparative 30 A′-5-9 F30FG 121.155 0.01 73 0.04 Example 5-2 Comparative 30 A′-5-9 JF122 110.7 71 0.02 530.03 Example 5-3

Discussion on the Results of the Examples and Comparative Examples

Example 5-1, Example 5-3 to Example 5-8, Example 5-10, and Example 5-11are olefin-based resin compositions obtained by suitably blending 100parts by weight each of polar-group-containing olefin copolymers(A′-5-1, A′-5-3, A′-5-4, A′-5-6, and A′-5-7) with 1-99,900 parts byweight of any of olefin-based resins having a melting point of 124° C.or lower, and show satisfactorily high adhesiveness to the fluororesin.These resin compositions further have an adhesion strength ratio of 1.0or higher, showing that the effect of improving adhesiveness wassufficient. Moreover, Example 5-1, Example 5-3 to Example 5-8, andExample 5-11, in which olefin-based resins having a melting point of110° C. or lower have been blended, have an adhesion strength ratio,regarding adhesion to the fluororesin, of 2.0 or higher, showing thatthe adhesiveness-improving effect was remarkable.

Comparative Example 5-1, for which an olefin-based resin having amelting point higher than 124° C. was used, shows considerably lowadhesiveness to the fluororesin and has an adhesion strength ratio lessthan 1.0. No adhesiveness-improving effect was observed therein.

Comparative Example 5-2 and Comparative Example 5-3 are olefin-basedresin compositions likewise obtained by suitably blending 100 parts byweight of a polar-group-containing olefin copolymer (A′-5-9) produced bya high-pressure radical process with 1 to 99,900 parts by weight ofeither of olefin-based resins having a melting point within a specificrange, and showed an exceedingly low strength of adhesion to thefluororesin and a poor adhesion strength ratio. This fact showed thatthe polar-group-containing olefin copolymer of the invention improvesgreatly in adhesiveness when blended with an olefin-based resin having amelting point of 124° C. or lower, as compared withpolar-group-containing olefin copolymers produced by a high-pressureradical polymerization process, and that so long as 100 parts by weightof the polar-group-containing olefin copolymer according to theinvention is blended with 1 to 99,900 parts by weight of an olefin-basedresin having a melting point of 124° C. or lower, a highadhesiveness-improving effect is obtained.

The reason why the olefin-based resin compositions obtained by blendinga polar-group-containing olefin copolymer having a linear structure withan olefin-based resin having a melting point of 124° C. or lower showimproved adhesiveness as compared with the polar-group-containing olefincopolymer by itself is not clear. It is, however, thought that thepolar-group-containing olefin copolymer contained in each olefin-basedresin composition probably needs to have a linear molecular structure.The adhesiveness of an olefin copolymer to highly polar materials ofdifferent kinds is evaluated in terms of numerical values measured in apeel test such as that shown in JIS K6854, 1-4 (1999) “Adhesives—PeelAdhesion Strength Test Method”. It is, however, thought that such anumerical value measured by this method is the sum of the chemical andphysical bonding power exerted at the interface between the differentmaterials and the cohesive power or stress for deformation of eachmaterial. The polar-group-containing olefin copolymer produced by ahigh-pressure radical polymerization process has a highly branchedmolecular structure which contains short-chain branches and long-chainbranches in too large an amount. It is known that olefin-based resinshaving such a structure are inferior in mechanical property, cohesivepower, impact resistance, etc. to olefin-based resins having a linearstructure, and it is presumed that polar-group-containing olefincopolymers also have this tendency. It is thought that even when apolar-group-containing olefin copolymer produced by a high-pressureradical polymerization process has sufficient chemical bonds withmaterials of different kinds, the cohesive power thereof is poorer thanthat of polar-group-containing olefin copolymers having a linearstructure, resulting in a decrease in adhesiveness.

Example 5-2, Example 5-9, and Example 5-12 are olefin-based resincompositions obtained by blending polar-group-containing olefincopolymers (A′5-2, A′-5-5, and A′-5-8), in a proportion within aspecific range, with any of olefin-based resins having a melting pointof 124° C. or lower, and show sufficient adhesiveness to the polyamide.These resin compositions have an adhesion strength ratio of 2.0 orhigher, showing that the effect of improving adhesiveness wasremarkable. This fact showed that the adhesiveness-improving effect inolefin-based resin compositions obtained by blending apolar-group-containing olefin copolymer having a linear structure withan olefin-based resin having a melting point of 124° C. or lower isproduced in application to bases which are not limited to specific ones.

Example 5-1 to Example 5-12 are compositions in which each ofpolar-group-containing olefin copolymers has been compounded with any ofolefin-based resins having a melting point of 124° C. or lower. It wasdemonstrated that a sufficient adhesiveness-improving effect is obtainedin the olefin-based resin compositions regardless of the MFR or theolefin-based resin, the kinds of the polymerized monomers, and theproportion.

The predominance and rationality of the configurations of the invention(characterizing features of the invention) and the superiority thereofto prior-art techniques have been rendered clear by the satisfactoryresults of the Examples given above and by the comparisons between theExamples and the Comparative Examples.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof. This application is basedon a Japanese patent application filed on Mar. 27, 2013 (Application No.2013-067402), a Japanese patent application filed on Mar. 27, 2013(Application No. 2013-067409), a Japanese patent application filed onJun. 26, 2013 (Application No. 2013-133857), a Japanese patentapplication filed on Feb. 28, 2014 (Application No. 2014-039324), and aJapanese patent application filed on Feb. 28, 2014 (Application No.2014-039335), the contents thereof being incorporated herein byreference.

INDUSTRIAL APPLICABILITY

The polar-group-containing olefin copolymer (A) of the invention, themultinary polar olefin copolymer (B) of the invention, and theolefin-based resin composition (D), olefin-based resin composition (D′),and olefin-based resin composition (D″) of the invention, which eachinclude the polar-group-containing olefin copolymer and an olefin-basedresin, have high adhesiveness to other bases and have made it possibleto produce industrially useful layered products. The resin compositionswhich can be produced by the invention are excellent in terms of notonly adhesiveness but also mechanical and thermal property, and areapplicable as useful multilayered molded objects. These resincompositions, after laminated to various bases, are utilized extensivelyin the field of packaging materials and packaging containers, the fieldof industrial materials such as fibers, pipes, fuel tanks, hollowvessels, and drum cans, the field of construction materials such aswater cutoff materials, the electronic field including members forelectronic or domestic electrical appliances, the electrical-wire fieldincluding electrical wires and cables, etc.

1. A polar-group-containing olefin copolymer which comprises 99.999 to80 mol % of structural units derived from at least one of ethylene andα-olefin having 3 to 20 carbon atoms and 20 to 0.001 mol % of structuralunits derived from at least one polar-group-containing monomer whichcontains an epoxy group and is represented by the following structuralformula (I) or following structural formula (II), thepolar-group-containing olefin copolymer being a random copolymerobtained by copolymerization in the presence of a transition metalcatalyst and having a linear molecular structure:

(In structural formula (I), R¹ represents a hydrogen atom or an alkylgroup having 1 to 10 carbon atoms, and R², R³, and R⁴ each independentlyrepresent a hydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R² to R⁴being the following epoxy-group-containing specific functional group:Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure comprising a carbon atom, an oxygenatom, and a hydrogen atom),

(In structural formula (II), R⁵ to R⁸ each independently represent ahydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R⁵ to R⁸being the following epoxy-group-containing specific functional group,and m is 0 to 2: Specific functional group: a group which essentiallycontains an epoxy group and has a molecular structure comprising acarbon atom, an oxygen atom, and a hydrogen atom)
 2. Thepolar-group-containing olefin copolymer according to claim 1, which hasa melting point of 50 to 140° C., the melting point being thetemperature corresponding to a maximum peak in an endothermic curvedetermined by differential scanning calorimetry (DSC).
 3. Thepolar-group-containing olefin copolymer according to claim 1, whereinthe amount of aluminum (Al) in the polar-group-containing olefincopolymer is 0 to 100,000 μg per g of the copolymer.
 4. Thepolar-group-containing olefin copolymer according to claim 1, which hasa weight-average molecular weight (Mw), as determined by gel permeationchromatography (GPC), of 1,000 to 2,000,000.
 5. Thepolar-group-containing olefin copolymer according to claim 1, which hasa weight-average molecular weight (Mw), as determined by gel permeationchromatography (GPC), of 33,000 to 2,000,000.
 6. Thepolar-group-containing olefin copolymer according to claim 1, whereinthe transition metal catalyst is a transition metal catalyst whichcomprises a chelatable ligand and a Group-5 to Group-11 metal.
 7. Thepolar-group-containing olefin copolymer according to claim 1, whereinthe transition metal catalyst is a transition metal catalyst comprising:palladium or nickel metal; and a triarylphosphine or triarylarsinecompound coordinated thereto.
 8. A polar-group-containing multinaryolefin copolymer comprising: units of one or more nonpolar monomers (X1)selected from ethylene and α-olefins having 3 to 10 carbon atoms; unitsof one or more polar monomers (Z1) selected from monomers having anepoxy group; and units of any one or more non-cyclic or cyclic monomers(Z2) (with the proviso that at least one kind of units of X1, at leastone kind of units of Z1, and at least one kind of units of Z2 areessentially contained), the polar-group-containing multinary olefincopolymer being a random copolymer obtained by copolymerization in thepresence of a transition metal catalyst and having a linear molecularstructure.
 9. The polar-group-containing multinary olefin copolymeraccording to claim 8, which has a ratio of weight-average molecularweight (Mw) to number-average molecular weight (Mn), as determined bygel permeation chromatography (GPC), in the range of 1.5 to 3.5.
 10. Thepolar-group-containing multinary olefin copolymer according to claim 8,which has a melting point Tm (° C.) satisfying 50<Tm<128−6.0[Z1](wherein [Z1] (mol %) is the content of monomer units derived from Z1),the melting point being the temperature corresponding to a maximum peakin an endothermic curve determined by differential scanning calorimetry(DSC).
 11. The polar-group-containing multinary olefin copolymeraccording to claim 8, wherein the content of the units of one or morepolar monomers (Z1) selected from monomers having an epoxy group is0.001 to 20.000 mol %.
 12. The polar-group-containing multinary olefincopolymer according to claim 8, wherein the units of one or morenonpolar monomers (X1) are ethylene units.
 13. Thepolar-group-containing multinary olefin copolymer according to claim 8,wherein the transition metal catalyst is a transition metal catalystwhich comprises a chelatable ligand and a Group-5 to Group-11 metal. 14.The polar-group-containing multinary olefin copolymer according to claim8, wherein the transition metal catalyst is a transition metal catalystcomprising: palladium or nickel metal; and a triarylphosphine ortriarylarsine compound coordinated thereto.
 15. An olefin-based resincomposition comprising: a polar-group-containing olefin copolymer (A′)and an olefin-based resin (C), the polar-group-containing olefincopolymer (A′) being a random copolymer having a linear molecularstructure and obtained by copolymerizing at least one of ethylene andα-olefin having 3 to 20 carbon atoms with a polar-group-containingmonomer containing an epoxy group in the presence of a transition metalcatalyst, wherein the amount of the olefin-based resin (C) incorporatedis 1 to 99,900 parts by weight per 100 parts by weight of thepolar-group-containing olefin copolymer (A′).
 16. The olefin-based resincomposition according to claim 15, wherein the polar-group-containingmonomer containing an epoxy group is a polar-group-containing monomercontaining an epoxy group, represented by the following structuralformula (I) or following structural formula (II):

(In structural formula (I), R¹ represents a hydrogen atom or an alkylgroup having 1 to 10 carbon atoms, and R², R³, and R⁴ each independentlyrepresent a hydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R² to R⁴being the following epoxy-group-containing specific functional group,Specific functional group: a group which essentially contains an epoxygroup and has a molecular structure comprising a carbon atom, an oxygenatom, and a hydrogen atom),

(In structural formula (II), R⁵ to R⁸ each independently represent ahydrogen atom, a hydrocarbon group, or the followingepoxy-group-containing specific functional group, any one of R⁵ to R⁸being the following epoxy-group-containing specific functional group,and m is 0 to 2: Specific functional group: a group which essentiallycontains an epoxy group and has a molecular structure comprising acarbon atom, an oxygen atom, and a hydrogen atom)
 17. The olefin-basedresin composition according to claim 15, wherein in thepolar-group-containing olefin copolymer (A′), the amount of structuralunits derived from at least one of ethylene and α-olefin having 3 to 20carbon atoms is 99.999 to 80 mol % and the amount of structural unitsderived from the polar-group-containing monomer containing an epoxygroup is 20 to 0.001 mol %.
 18. The olefin-based resin compositionaccording to claim 15, wherein the olefin-based resin (C) is at leastone of a homopolymer and a copolymer, the homopolymer and the copolymerbeing obtained by polymerizing a monomer selected from at least one ofethylene and α-olefin having 3 to 20 carbon atoms.
 19. The olefin-basedresin composition according to claim 15, wherein the olefin-based resin(C) is either an ethylene homopolymer or a copolymer of ethylene withα-olefin having 3 to 20 carbon atoms.
 20. The olefin-based resincomposition according to claim 15, wherein the polar-group-containingolefin copolymer (A′) has a melting point in the range of 50 to 140° C.,the melting point being the temperature corresponding to a maximum peakin an endothermic curve determined by differential scanning calorimetry(DSC).
 21. The olefin-based resin composition according to claim 15,wherein the polar-group-containing olefin copolymer (A′) is a copolymerobtained by polymerization in the presence of a transition metalcatalyst of a Group-5 to Group-11 metal having a chelatable ligand. 22.The olefin-based resin composition according to claim 15, wherein thepolar-group-containing olefin copolymer (A′) is a copolymer obtained bypolymerization in the presence of a transition metal catalyst whichcomprises palladium or nickel metal and a triarylphosphine ortriarylarsine compound coordinated thereto.
 23. The olefin-based resincomposition according to claim 15, wherein the olefin-based resin (C)has a density, as measured in accordance with JIS K7112, in the range of0.890 to 1.20 g/cm³.
 24. The olefin-based resin composition according toclaim 15, wherein the olefin-based resin (C) has a melting point in therange of 90 to 170° C., the melting point being the temperaturecorresponding to a maximum peak in an endothermic curve determined bydifferential scanning calorimetry (DSC).
 25. The olefin-based resincomposition according to claim 15, wherein the melting point ofolefin-based resin (C), which is the temperature corresponding to amaximum peak in an endothermic curve determined by differential scanningcalorimetry (DSC), is in the range of 119 to 170° C.
 26. Theolefin-based resin composition according to claim 15, which has a heatof fusion ΔH, as determined by differential scanning calorimetry (DSC),in the range of 80 to 300 J/g.
 27. The olefin-based resin compositionaccording to claim 15, wherein the olefin-based resin (C) has a meltingpoint in the range of 30 to 124° C., the melting point being thetemperature corresponding to a maximum peak in an endothermic curvedetermined by differential scanning calorimetry (DSC).
 28. An adhesivewhich comprises the polar-group-containing olefin copolymer according toclaim 1, the polar-group-containing multinary olefin copolymer accordingto claim 8, or the olefin-based resin composition according to claim 15.29. A layered product which comprises: the polar-group-containing olefincopolymer according to claim 1, the polar-group-containing multinaryolefin copolymer according to claim 8, or the olefin-based resincomposition according to claim 15; and a base layer.
 30. The layeredproduct according to claim 29, wherein the base layer comprises at leastone member selected from olefin-based resins, highly polar thermoplasticresins, metals, vapor-deposited films of inorganic oxide, paper,cellophane, woven fabric, and nonwoven fabric.
 31. The layered productaccording to claim 29, wherein the base layer comprises at least onemember selected from polyamide-based resins, fluororesins,polyester-based resins, and ethylene/vinyl alcohol copolymers (EVOH).